US Airways has a daily flight to Barcelona and Madrid out of PHL (6.5hr flight with tailwind). Red eye flight that leaves typically around 6-7pm EST. The planes are A330's that I think make the flight from PHL to MAD/BAR and lands around 0800-0900 local time. Plane gets turned around for a few hours and heads back to PHL 1200-1300 local time and arrives in PHL at 3pm EST (7.5hr flight going into the wind).
I just took this flight on a weds night and returned on saturday. Envoy class is sooo money on this flight!