Doping semiconductor nanowires (NWs) for altering their electrical and optical properties is a critical strategy for tailoring the performance of nanodevices. ZnO NWs grown by hydrothermal method are pervasively used in optoelectronic, photovoltaic, and piezoelectric energy-harvesting devices. We synthesized in situ Cl-doped ZnO NWs with metallic conductivity that would fit seamlessly with these devices and improve their performance. Possible Cl doping mechanisms were discussed. UV–visible absorption spectroscopy confirmed the visible light transparency of Cl-doped ZnO NWs. Cl-doped ZnO NW/TiO₂ core/shell-structured photoelectrochemical (PEC) anode was fabricated to demonstrate the application potential of highly conductive ZnO NWs. Higher photocurrent density and overall PEC efficiency compared with the undoped ZnO NW-based device were achieved. The successful doping and low resistivity of ZnO could unlock the potential of ZnO NWs for applications in low-cost flexible transparent electrodes.