Precise control of the topology of metal nanocrystals and appropriate modulation of the metal-semiconductor heterostructure is an important way to understand the relationship between structure and material properties for plasmon-induced solar-to-chemical energy conversion. Here, a bottom-up wet chemical approach to synthesize Au/Ni2P heterostructures via Pt-catalyzed quasi-epitaxial overgrowth of Ni on Au nanorods (NR) is presented. The structural motif of the Ni2P is controlled using the aspect ratio of the Au NR and the effective micelle concentration of the C(16)TAB capping agent. Highly ordered Au/Pt/Ni2P nanostructures are employed as the photoelectrocatalytic anode system for water splitting. Electrochemical and ultrafast absorption spectroscopy characterization indicates that the structural motif of the Ni2P (controlled by the outer-shell deposition of Ni) helps to manipulate hot electron transfer during surface plasmon decay. With optimized Ni2P thickness, Pt-tipped Au NR with an aspect ratio of 5.2 exhibits a geometric current density of 10 mA cm(-2) with an overpotential of 140 mV. The photoanode displays unprecedented long-term stability with continuous chronoamperometric performance of 50 h at an input potential of 1.5 V with over 30 days. This work provides definitive guidance for designing plasmonic-catalytic nanomaterials for enhanced solar-to-chemical energy conversion.