There are tons of openers I love. These are a few off the top of my head in no particular order.
The opening drum fill to Only Shallow gets me every time. David Bowie's Station to Station is fantastic. Summer Babe comes to mind. Disorder - Joy Division, Welcome to the Working Week - Elvis Costello, Schizophrenia - Sonic Youth, Sunday Morning - The Velvet Underground, Cygnus... Vismund Cygnus - The Mars Volta, Untitled - Interpol, Arcarsenal - At the Drive-In, The Queen Is Dead - The Smiths.