Solid films of C60 deposited on CaF2 under ultrahigh vacuum show luminescence in the 700-1100-nm spectral range at 20 K. A 1400-cm-1 progression in the a(g) soccerball pentagonal pinch mode is observed. The low-temperature absorption spectrum exhibits similar fine structure. The characterization of vibronic splittings in the ground and emitting state and the transition intensity mechanism are discussed.