The current study reports a novel inorganic/organic light-emitting diode (LED), consisting of zinc oxide (ZnO) nanorod arrays and poly(2-methoxy, 5-octoxy)-1,4-phenylenevinylene (MOPPV). ZnO nanorod arrays passivated using polyacrylamide (PAM) with 70 nm diameter were successfully prepared by a simple polymer-assisted chemical method. Enhancement of the ZnO defect emission is caused by PAM passivation, as observed in photoluminescence spectra. Infrared absorption spectra reveal that PAM is chemically or physically adsorbed on the surfaces of ZnO nanorod arrays. The electroluminescence (EL) spectrum shows bluish light at 406 nm from ZnO transition emission, and light emission with center at 600 nm from exciton emission in MOPPV. The potential EL mechanism is electron transition to zinc vacancy in PAM/ZnO nanorod arrays, and exciton radiation luminescence in MOPPV film. This novel PAM/ZnO-MOPPV device may be helpful to promote development of multicolor LEDs.