A Sb-doped ZnO microrod array was fabricated on an Al-doped ZnO thin film by electrodeposition. Strong violet luminescence, originated from free electron-to-acceptor level transitions, was identified by temperature-dependent photoluminescence measurements. This acceptor-related transition was attributed to substitution of Sb dopants for Zn sites, instead of O sites, to form a complex with two Zn vacancies (VZn), the SbZn-2VZn complex. This SbZn-2VZn complex has a lower formation energy and acts as a shallow acceptor which can induce the observed strong violet luminescence. The photoresponsivity of our ZnO p-n homojunction device under a negative bias demonstrated a nearly 40-fold current gain, illustrating that our device is potentially an excellent candidate for photodetector applications in the ultraviolet wavelength region.