We report the synthesis of vertically aligned ZnO/a-Si core-shell nanowire arrays (ZnO nanowires coated with amorphous silicon) through chemical vapor deposition. The core-shell heterostructured nanowires possessed uniform morphology and the thickness of the amorphous silicon shells could be controlled easily by tuning the deposition duration and temperature. The core-shell heterostructured nanowires exhibited enhanced antireflection and absorption performance as well as tunable PL properties. Because the individual ZnO/a-Si nanowires showed p-type characteristics and the ZnO cores were n-type semiconductors, the core-shell nanowires formed p-n junctions naturally.