Because I'm bored, and I just read (and watched) High Fidelity.
And I'm not limiting it to just five, because that's just way too much thinking for 2am.
Somewhat random order, as they come to me ...
The Cure - "In Between Days", from "The Head On The Door"
The Cure - "The Kiss", from "Kiss Me, Kiss Me, Kiss Me"
The Doors - "Break on Through (To the Other Side)", from "The Doors"
The Doors - "Roadhouse Blues", from "Morrison Hotel"
Wu Tang Clan - "Bring Da Ruckus", from "Enter the Wu-Tang (36 Chambers)"
Violent Femmes - "Blister in the Sun", from "Violent Femmes"
Smashing Pumpkins - "Cherub Rock", from "Siamese Dream"
Led Zeppelin - "Whole Lotta Love", from "Led Zeppelin II"
Led Zeppelin - "Immigrant Song", from "Led Zeppelin III"
Led Zeppelin - "The Song Remains the Same", from "Houses of the Holy"
Pixies - "Debaser", from "Doolittle"
Bob Dylan - "Blowin' In The Wind", from "The Freewheelin' Bob Dylan"
Bob Dylan - "The Times They Are a-Changin'", from "The Times They Are a-Changin'"
Bob Dylan - "Subterranean Homesick Blues", from "Bringing It All Back Home"
Bob Dylan - "Like a Rolling Stone", from "Highway 61 Revisited"
Bob Dylan - "Rainy Day Women #12 & 35", from "Blonde on Blonde"
Bob Dylan - ""Tangled Up in Blue", from "Blood on the Tracks"
Bob Dylan - "Hurricane", from "Desire"
Bright Eyes - "If Winter Ends", from "Letting Off The Happiness"
Bright Eyes - "At The Bottom Of Everything", from "I'm Wide Awake, It's Morning"
The White Stripes - "Dead Leaves and the Dirty Ground", from "White Blood Cells"
Radiohead - "Packt Like Sardines in a Crushd Tin Box", from "Amnesiac"
Nirvana - "Smells Like Teen Spirit", from "Nevermind" (unavoidable, that one)
Tool - "Stinkfist", from "Ænima"
The Beatles - "A Hard Day's Night", from "A Hard Day's Night"
Björk - "Human Behaviour", from "Debut"
Björk - "Army Of Me", from "Post"
Björk - "Hunter", from "Homogenic"
The Decemberists - "The Infanta", from "Picaresque"
The Chemical Brothers - "Block Rockin' Beats", from "Dig Your Own Hole"
Blur - "Girls & Boys", from "Parklife"
This isn't interesting enough to put any more effort into. Also, there'd be quite a few Hip-Hop albums on this list if they didn't all have intro tracks.