The photoelectrocatalytic (PEC) technique has attracted much attention to getting clear energy and environmental purification. Simultaneous reactions of solar energy generation could be used to apply for practical applications to maximize the functionality of reactor systems. Herein, we crafted a self-driving photoelectrocatalytic reactor system, comprising platinum (Pt) modified p-Si nanowires (Pt/Si-NWs) as a photocathode and TiO nanotube arrays (TiO-NTAs) as a photoanode for synergistic H evolution and water purification, respectively. Hydrogen evolution in the cathode chamber and environmental remediation in the anode chamber were achieved with the aid of appropriate bandgap illumination and self-built bias voltage. The mismatch of Fermi levels between TiO-NTAs and Si-NWs reduced the recombination rates of photoinduced electrons and holes through the formation of Z scheme and inner electric filed. The synergistic PEC reactions exhibited much higher activities than those achieved using other systems so far. This basic principal could be applied for fabricating other PEC reactors in photoelectro conversion devices and be established as design guidelines for reactors to maximize the PEC performance.