The surface structures and the electronic states of poly(3-hexylthiophene) (P3HT) and phenyl-C-61-butyric acid methyl ester (PCBM) blend films are studied by using doubly resonant infrared-visible sum frequency generation (DR-SFG) spectroscopy. The SFG spectra of P3HT indicate the co-existence of the ordered and disordered P3HT at the interface. In the P3HT:PCBM blend film, the peak located at 1460cm(-1), which is originated from the charge transfer state of PCBM, is observed.