To date, most metal oxide-based photocathodes used in photoelectrochemical cells for water splitting contain copper cations in its composition, which can be reduced to metal Cu under cathodic bias leading to deactivation of the photoelectrode. Here, a Cu-free photocathode composed by a ternary heterostructure of Bi2O3/Al2Bi24O39/Al2Bi48O75 nanowires is reported with a narrow band gap energy (1.83 eV) and suitable conduction band edge potential (- 0.98 V-RHE) for water reduction to hydrogen. Photoelectrochemical measurements display that the highest photocurrent density of - 4.85 mA cm(-2) at 0 V-RHE under simulated sunlight is achieved by tuning the Bi:Al molar ratio of photocathode to 21:1. The photocurrent onset potential of the Bi2O3/BiAl oxides photoelectrode was estimated to be 0.57 V-RHE at pH 7, which is comparable to that of silicon. Controlled potential photoelectrolysis at 0 V-RHE showed a stable photocurrent of about - 2 mA cm(-2) for 2h of continuous operation. The H-2 measured at this time was 696 mu mol cm 2, which corresponds to a Faradaic efficiency of 93%. Finally, this work gives a new generation of Cu-free photocathodes and demonstrates a promising future of BiAl oxides in constructing photoelectrochemical devices for water splitting.