(1)Buffy Firsts: "Xander"
The first time Buffy meets Xander, it's "very suave, very not pathetic."
(2)Buffy Firsts: "Cordelia"
Buffy passes Cordelia's test and is officially not a loser, but Buffy can kinda guess who the real loser is... as in, Probably Not Willow.
(3)Buffy Firsts: "Giles"
Witness the very first time Buffy sets foot in the Sunnydale High library, and the very first time Giles overestimates Buffy's enthusiasm for slaying.
(4)Buffy Firsts: "Willow"
Awww! It's the first time Buffy and Willow talk and make a friend date! Little do they know they'll be saving the world in the very next episode.
(5)Buffy Firsts: "Angel"
When Buffy meets Angel in a dark alley... it's not quite love at first kick in the base of the skull.
(6)Buffy Firsts: "Slayage"
The first of many, many, manymanymany vampires dusted on BtVS.