Performance improvement of CdS nanorod arrays (NRA)/poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV) hybrid solar cells (HSCs) during the storage in ambient atmosphere has been demonstrated. An unusual photoluminescence (PL) enhancement was observed after MEH-PPV hybridizing with CdS NRA due to the abundance of S-vacancy-induced interface electron traps in CdS NRA, which was confirmed by temperature-dependent PL and charge transport analysis. By investigating on the time-resolved photoluminescence (TRPL) and current-voltage characteristics, we demonstrated that the performance improvement of CdS NRA/MEH-PPV HSCs was contributed to the co-effects of interface electron trap-oxygen interaction and MEH-PPV-oxygen interaction, and the contribution ratio between these two interactions was varied over time in air. (C) 2011 Elsevier B.V. All rights reserved.