Mirelurk king that has a crown and leads a "nation" of Lurks, Mantids.
A comical *nationality here* -accented Gecko follower!
A "Mages guild" of maniacs using energy weapons who think they are magical tools.
A robot/computer who says "I cant let you do that dave" during dialouge, and you can ask it why it called you dave(unless your name is Dave) and it says it mistook you for someone else, then lets you proceed.
CL commander who talks like Christopher Walken, wears gloriously decorated PA, and uses only boxing gloves because he is that hardcoe.
Crazed low-ranking CL soldier convinced he is immortal and wields a scrap sword, he keeps mentioning that "there can be only one"
A crazy survivalist ghoul who stocked up enough food in his basemant to survive 203 years without going outside, and you can coax him to go outside, when he does he looks at a devastated landmark/building, falls to his knees and says "You really did it, you blew it up!"
NCR officer who is obsessed with using old fashioned PSA's as catchphrases, regardless of the context or sense they make.
Random Gecko that is wearing robes that makes it look like a Jawa.