Zn 1−x Fe x O y nanocomposites have been investigated for bi-functional performance towards photoelectrochemical (PEC) and photocatalytic (PC) splitting of water to produce hydrogen. Prepared at varying Zn/Fe atomic ratio via co-precipitation through controlled addition of NH 4 OH to the aqueous solution of iron (III) nitrate nonahydrate [Fe(NO 3) 3 •9H 2 O] and zinc acetate dihydrate [(CH 3 •COO) 2 Zn•2H 2 O], followed by sintering in air at 800 °C, the nanocomposites were characterized by XRD, SEM, TEM, UV-Visible optical absorption, XPS, and Mössbauer spectral analysis. Shift in bandgap energy (E g) and alterations in microstructural characteristics and electrical properties, observed with change in sample-composition, significantly influenced hydrogen generation. Plausible reasons have been offered. The optimum conditions for hydrogen generation via PEC and PC routes, not being similar, have also been worked out.