An array of ZnO/Fe2O3 core-shell nanowires (NW) for the highly efficient absorption of light and carrier collection is developed for use in photoelectrochemical (PEC) water-splitting. The oriented NW architecture favors physical matching, providing a direct electron conduction pathway and reducing the diffusion length of photogenerated holes. This work involves a combination of spectral imaging, spectromicroscopy and in situ x-ray absorption spectroscopy; spectra are obtained under operando conditions. Direct investigation of oriented nanowires using polarization-dependent x-ray spectromicroscopy enables the determination of the relationship between anisotropic electronic orbitals and charge carrier water-splitting efficiency. The results of O K-edge STXM demonstrated that the ZnO/Fe2O3 core-shell NW exhibits strong anisotropy and thus provides higher electron-hole transport efficiency than bare ZnO. In situ XAS revealed that interfacial charge transfer between Fe 3d and Zn 4p states enhances the photoelectrochemical reaction in the ZnO/Fe2O3 core-shell NW. The photogenerated electrons of Fe2O3 are transferred from Fe 3d states to the Zn 4p state under photoelectrochemical conditions.