Silicon nanowires (SiNWs) opened up exciting possibilities in a variety of research fields due to their unique anisotropic morphologies, facile tuning capabilities, and accessible fabrication methods. The SiNW-based photoelectrochemical (PEC) conversion has recently been known to provide an efficiency superior to that of various photo-responsive semiconductor heterostructures. However, a challenge still remains in designing optimum structures to minimize photo-oxidation and photo-corrosion of the Si surface in a liquid electrolyte. Here, we report a simple method to synthesize hierarchically branched carbon nanowires (CNWs) on SiNWs utilizing copper vapor as the catalyst in a chemical vapor deposition (CVD) process, which exhibits outstanding photocatalytic activities for hydrogen generation along with excellent chemical stability against oxidation and corrosion. Thus, we believe that the CNW-SiNW photoelectrodes would provide a new route to developing high-performing cost-effective catalysts essential for advanced energy conversion and storage technologies.