The optimization of multiple interfaces in hematite (α-Fe2O3) based composites for photoelectrochemical water splitting to facilitate charge transport in the bulk is of paramount importance to obtain enhanced solar-to-fuel efficiency. Herein, we report the fabrication of ITO/Fe2O3/Fe2TiO5/FeNiOOH multi-layer nanowires and a series of systematic experiments designed to elucidate the mechanism underlying the interfacial coupling effect of the quaternary hematite composite. The hierarchical ITO/Fe2O3/Fe2TiO5/FeNiOOH nanowires display photocurrents that are more than an order of magnitude greater than those of pristine Fe2O3 nanowires (from 0.205 mA cm−2 to 2.2 mA cm−2 at 1.23 V vs. RHE and 1 Sun), and higher than those of most of the recently reported state-of-the-art hematite composites. Structural, compositional and electrochemical investigations disclose that the surface states (SS) are finely regulated via the atomic addition of an Fe2TiO5 layer and FeNiOOH nanodots, while the upgrading of back contact conductivity and charge donor densities originate from the epitaxial relationship and enhanced Sn doping contributed from the ITO underlayer. We attribute the superior water oxidation performance to the interfacial coupling effect of the ITO underlayer (Sn doping and back contact conductivity promoter), the atomic level Fe2TiO5 coating (Ti doping, surface state density and energy level modulation) and the FeNiOOH nanodot electrocatalyst (regulating surface state energy level). Our work suggests an effective pathway for rational designing of highly active and cost-effective integrated photoanodes for photoelectrochemical water splitting.