This study aimed to rationally design the novel Bi2Te3 implanted ZnO (Bi2Te3@ZnO) thin films using simultaneous RF and DC magnetron sputtering technique. Herein, we explored the electrolyte interface effect (0.1 M of KOH, KCl, Na2SO3 and Na2SO4) on ZnO and Bi2Te3@ZnO towards highly stable PEC water splitting activity for the first time. Specifically, morphological evolution and electrolyte ion diffusion properties play a crucial role in realizing the prolonged charge carrier lifetime. Moreover, Bi2Te3@ZnO is highlighted with unique nanocone-shaped morphology compared to flake-like ZnO. Also, constructive interfacial interaction was observed between Bi2Te3 and ZnO. As a result, Bi2Te3@ZnO demonstrated superior and highly stable photocurrents in the KOH electrolyte compared to KCl, Na2SO3 and Na2SO4 electrolytes. Precisely, Bi2Te3@ZnO triumphed highly stable photocurrents about 7.93 × 10–4 A cm−2 compared to ZnO (6.02 × 10–4) at +0.4 V under solar light in KOH electrolyte. Accordingly, Bi2Te3@ZnO achieved remarkable photoconversion efficiency (η) about 0.65 %, which is enabled by the strengthened intimate interaction between Bi2Te3 and ZnO. Furthermore, we compared the PEC activity under visible light (UV cut-off solar light). These results highlighted that the photoconversion efficiency difference between Bi2Te3@ZnO and ZnO (about 4 times) under visible light is relatively higher than solar light (1.3 times) in KOH. Thus, we proposed different charge carrier generation mechanisms of Bi2Te3@ZnO under solar and visible light. Therefore, intimate interfacial interaction, surface modification, ion diffusion and photoelectrode-electrolyte interaction are key parameters to enhance the PEC activity. Overall, rational design of the transition metal oxide/thermoelectric material interface using Bi2Te3@ZnO composite paves a new path towards highly stable photoanode during PEC water splitting activity in the KOH electrolyte environment.