My wife just asked me this and it came to me pretty quickly: Black Dog, the opening track from IV. Since thinking more about it, I’m wondering if I was a bit hasty. I mean, there’s Kashmir and Bron-Yr-Aur from Physical Graffiti to consider. And don’t forget the epic Battle of Evermore on IV. So off I went on a listening spree, and turns out I was right after all. It’s Black Dog right enough. Must be one of the best openers on any album, ever!
The good lady picked D’Yer Mak’er from Houses of the Holy straight off the bat and a very good choice it is, too. Got to love the Led Zep!