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First Songs on First Albums

Finding My Way - Rush (Rush)
Good Times Bad Times - Led Zeppelin (Led Zeppelin)
Dimension - Wolfmother (Wolfmother)
It is Not Meant to Be - Tame Impala (Innerspeaker)
Next to You - The Police (Outlandos d'Amour)
Blew - Nirvana (Bleach)
Sunburn - Muse (Showbiz)
Purple Haze - The Jimi Hendrix Experience (Are You Experienced)
I Feel Free - Cream (Fresh Cream)
I Saw Her Standing There - The Beatles (Please Please Me)
 
One of These Days - Pink Floyd, Meddle

Meddle was not even close to being Pink Floyd's first album, that would be Piper at the Gates of Dawn. Meddle was like 5th, 6th if you count the More soundtrack as an official album.

Stand Up and Shout by Dio off of Holy Diver is a good one.

But I have to go with Black Sabbath Black Sabbath Black Sabbath.

Of all the great first songs out there, that one stands the test of time and remains one of the greatest metal songs, hell, one of the greatest rock and roll songs period. And the band kept that stuff up for like 5 records in a row. Tremendous power.
 
Bob Dylan - S/T - You're No Good: Humble beginnings, no doubt.

Slayer - Show No Mercy - Evil Has No Boundaries: Absolutely diabolical.

Minutemen - Paranoid Time - Validation: Explosive, way outta left-field punk that got you hooked right from the get-go.

Pink Floyd - Piper at the Gates of Dawn - Astronomy Domine: Holy hell, talk about a head spinner.

The Beach Boys - Surfin' Safari- Surfin' Safari: Probably the first rock song I ever heard, and a great slice of '60s Americana.

Elvis Presley - S/T - Blue Suede Shoes: 'Nuff said.

Bad Brains - S/T - Sailin' On: Furious opener to one of the best hardcore punk tapes of the '80s.

Anthrax - Fistful of Metal - Deathrider: This album sounds nothing like any other one of theirs, but I've always loved Neil Turbin's voice on this.

13th Floor Elevators - The Psychedelic Sounds of... - You're Gonna Miss Me: Texas garage rock anthem.

Kiss - S/T - Strutter: Say what you want about 'em, these guys had some good tunes, this being one of my favorites. Gotta love that drum intro!

Blue Cheer - Vincebus Eruptum - Summertime Blues: Embryonic heavy metal take on a rock 'n roll classic.

Vanilla Fudge - S/T - Ticket to Ride: Psychedelic and heavy as hell, best cover band ever!

Wu-Tang Clan - Enter The Wu-Tang (36 Chambers) - Bring Da Ruckus: The east coast scene would never be the same again.

Mötley Crüe - Too Fast for Love - Live Wire: Kick-ass hard rock that wastes no time getting started; these first two albums were like a bat outta hell.

Fleetwood Mac - S/T - My Heart Beat Like a Hammer: Not exactly a standout track of this period, but definitely set the tone for the first two LPs.

Mike Watt - Ball-Hog or Tugboat? - Big Train: '90s classic, Mike at his Mike-est.

Heart - Dreamboat Annie - Magic Man: FM staple, what a groovy way to start a rock record.
 
I Feel Free was the first track on the U.S. release of Fresh Cream, but did not appear on the U.K. release of the album. I Feel Free was released as a single, and in those days U.K. album releases generally didn't include singles. The first track on the U.K. version of Fresh Cream was N.S.U. "Driving in my car, smoking my cigar / The only time I'm happy's when I play my guitar."