For me? Wash and Joyce would be the top as well.
'Harm's Way'
Buffy and Angel 1: BUFFYNANGLE4EVA!!!!!1!
Is it better the second time around? Or the third? Or tenth? This is the place to come when you have a burning desire to talk about an old episode that was just re-run.
I think for me it was actually Buffy, at the end of Season 5, closely followed by Joyce. I remember feeling actually physically ill for a couple of days following both of those deaths, especially since I totally, despite about 150 million elements of foreshadowing, did not think Buffy would die. And when she did, I really thought that they wouldn't bring her back-- that they might do some body switcheroo or something and have SMG playing Faith or the Buffy bot or something.
I think part of the reason it hit me so hard is that I pretty much fell for Buffy during Restless, discovered the Buffistas and really the internet, mainlined all of the series I could get my hands on, all in that one season. And then she died!
I think because it was my first exposure to Jossverse deaths, I'm going with JCal as the one that hit me the hardest... with the effect it had on Giles and everyone. Willow and Buffy through the window, and then Buffy and Giles at the end. Oof. (Which is not to say that Joyce's death didn't affect them, der, but I'm just saying, I was more prepared for that sort of thing by the time The Body rolled around.)
I'm saddest about Wash. I love Wash, and Wash and Zoe, and Zoe, and that one kills me.
I think that Jenny Calendar hit me the hardest. It was so unexpected, and so cruel. I think that it was really the first time that the death that surrounded them really touched them.
Wesley's was the saddest, I think.
I watched Angel long after broadcast. When Doyle died I went on imdb to see what Glenn Quinn was up to lately. Finding out the actor was dead too left me feeling hollow for days. I still get choked up when I see him on Roseanne reruns.
Wesley's death was the saddest to me, because of the futility. Gutting.
The most initially shocking was Jenny Calendar's, for the reasons Vortex listed. It was the first time a character we'd come to care about really *died*, and the image of Angel carelessly, offhandedly, cheerfully doing the deed lingers in the mind's eye.
Joyce was next. We'd lost people before, but this time it affected everyone more deeply than Jenny's death. This was *mom*, the loss struck closer to the heart, and the reverberations were felt longer by everybody.
Tara, for those who loved or liked her, was between shocking and saddest. A character who sought only to help, who was kind and funny and had slid sideways into the affections of most of us and made a place there, ripped untimely from Willow and from us, without warning or justification. Whedon at his life-simulating best, the bastard.
Buffy's was shocking, but not a surprise. The networks-switching was a worry, it was easy to give in to the thought that maybe SMG was tired and wanted out of her contract, or that the show on the new network would be structured without Buffy. It was such a group-minded thing, I know the board here was in a glum and apprehensive mood for awhile, trying to process the knowledge that "Buffy's dead. "She saved the world. A lot."
Wash's death scene shocked me completely out of the movie, out of the narrative, out of the 'verse. I've come to accept that this is how Whedon wanted the story to go. I still don't believe Wash is gone. I haven't rewatched Serenity on dvd more than once to make sure the disc was okay. I rewatch Firefly 2-3 times a year. I'm sure Firefly would have reached the same conclusion as Serenity, but it would have been organic and believeable, at least for me. There are many things to like about the movie and more to appreciate. Loss of character agency for most of the cast and Wash's death overbalance those positive things for me. I can't deal with that character death in context, because it never feels earned to me.
Of course, Whedon is a master at the completely unexpected whappiness of fate, so.
You know what? Even though I was totally spoiled for Angel's death, When I finally saw it, I still sat there thinking, "I can't believe they motherfucking did it!" But it excited me, that Joss would go there.
I think I was most emotionally affected by Joyce's, which surprised me, because I never really liked the character. Also Doyle, because he was such a great character, and the show was so new, even though I knew there was meta reasons for killing the charcter off. Doyle was the first kill that gave Tim his rep for killing off beloved characters.
Honestly - the death that shocked me the most? Was the woman Angel randomly killed after sleeping with Buffy. And then I spent the entire next episode waiting for them to find the solution to him losing his soul. And they didn't. That's when I knew I was in a whole other world than your average TV (though DS9 and Twin Peaks had pulled stuff similar enough that it wasn't a totally unprecedented type of plot twist).
I think Tara was the most shocking to me. Somehow, since Tara had already been mind-sucked in season 5, I sort of felt like she should get a pass on anything else happening to her. She'd passed the immunity challenge, ya know? So, yeah, shocking to me.
Sad, was Joyce. Too personally resonant as I saw it right before my mother passed away, while she was in chemo. So, it kinda felt like an omen and I could barely watch it. I think I nearly threw up when Buffy did.
When Doyle died I went on imdb to see what Glenn Quinn was up to lately. Finding out the actor was dead too left me feeling hollow for days. I still get choked up when I see him on Roseanne reruns.
This. I saw it earlier, but never thought to look him up until I had the DVDs. I was hoping to find the DVDs for his British series, but no such luck. Quinn was just brilliant, and I'm still saddened that he's no longer with us.
Of the TV deaths, I think that most hit me hard. Joss and company are good at that. I was more saddened, perhaps, by some of the others, but Joyce's felt the most real. For the others, I was transported to the verse, and saddened there. For Joyce's, I could well imagine that was my mom, and I was saddened here, at home.