The effects of post-deposition heat treatments on MOCVD-ZnO/Dip CdS/Selenized CuInSe2, (CIS) thin film solar cells were investigated by photoluminescence (PL) measurements. PL measurements indicate the interactions between extrinsic oxygen and a native In-Cu antisite defect for the PL peak at about 1340 nm and the presence of a native O-Se defect as a donor site probably in the grain boundary for the broad PL peak centered at around 1420 nm. Applying the post-deposition annealing of 150 degrees C for 30 min. in air after CdS deposition, 10.3% efficiency was achieved with the CIS thin film absorber selenized in vacuum with elementary Se vapor.