"HT" The opening theme to Trigun.
"Cold Day in July" by the Dixie Chicks. Either Vash or Knives, after the July incident. Largely for the title, but some of the lines fit surprisingly well.
"Brothers Unaware" Vash and his inability to kill.
"Sin Wagon" by the Dixie Chicks. Partly because some of the lines remind of Vash leaving Knives, partly because it's about drinking, but mostly because it inspired my friend Draqonelle to draw the infamous "Vash & Nick in Saloon-girl Drag" picture.
"I'm Gonna Live Until I Die," by Frank Sinatra. Vash and his determinedly carefree lifestyle.
"I Take my Chances," by Mary Chapin Carpenter. For Vash, because he does.
"Me and My Shadow" by Frank Sinatra and Sammy Davis Jr. For Vash and Wolfwood, because it's the cutest best friends song ever written.
"Lord, I Have Made You a Place in my Heart," by Cry Cry Cry. For Wolfwood. If Nick has an image song, this is it.
"Fame" by Irene Cara (from the musical). Either for Midvalley, for obvious reasons, or for Vash, who is famous whether he wants to be or not.
"It's Probably Me" by Sting. Wolfwood, on his feelings for Vash.
"The Genocide Song," from episode 19 (English version). Because no Trigun playlist would be complete without it.
"Little Things" by Bush. The darker side of Vash and Wolfwood.
"Kryptonite" by Three Doors Down. Vash, especially later in the series.
"Drink With Me" from the musical Les Miserables. Vash and Wolfwood, obviously.
"Diamond Road" by Sheryl Crow. Vash, remembering Rem and Wolfwood. Because it's about friendship, love, and remembrance.
"Just Call Me Angel of the Morning" by the Pretenders. Millie to Wolfwood, in episode 23. The ultimate one-night-stand song.
"Hero" by Enrique Iglesias. Wolfwood to Vash. Yes, it's sappy and clich�d, but if anyone ever writes a lime/lemon songfic for them, this should be the song used. "Would you save my soul tonight?"
"Kyrie Eleison" from Mozart's Requiem Mass. For Wolfwood, at the end of episode 23. It means "Lord, have mercy," and this particular arrangement is meant to be sung at a funeral mass.
--can be used interchangeably with--
"Rakuen" from the Second Donut. (Trigun Soundtrack) Also for Wolfwood, actual music from episode 23.
"Everybody Hurts" by REM. Everybody hurts, especially Vash.
"Lucky Kid" by Sheryl Crow. A Knives and Vash song, about possession, obsession, and mistakes.
"Devil's Dance" by Metallica. Knives, trying to convince Vash to side with him.
"Waltz for Evita and Che" from the musical Evita. First suggested as a joke, it turned out on closer inspection to be a spookily appropriate Vash & Knives duet. Vash is Che and Knives, Evita for the first two verses, and then they switch parts.
"Bad Reputation," by Joan Jett. End of the series. Sort of a semi-rehabilitated Knives.