The seed layer annealing time strongly influences the textural and photo-activity of ZnO NWs. The average diameter and density of ZnO NWs were controlled to 47–70 nm and 46–70 NWs μm−2, respectively. ZnO NWs show promising application potential in solar-electrocatalytic water splitting under potential bias. The ZnO NWs with SL annealing time = 5 h achieve the highest HC-STH efficiency of 0.26% at 0.6 V.