Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting. Here, a novel TiO2/Cu2O/Al/Al2O3 photoelectrode is manufactured by depositing plasmonic nanoparticles of the non-noble metal Al on the surface of a TiO2/Cu2O core/shell heterojunction for the first time. The Al nanoparticles, which exhibit a surface plasmon resonance (SPR) effect and are substantially less expensive than noble metals such as Au and Ag, generate hot electron–hole pairs and amplify the electromagnetic field at the interface under illumination. The as-prepared TiO2/Cu2O/Al/Al2O3 photoelectrodes have an extended absorption range and enhanced carrier separation and transfer. Their photocurrent density of 4.52 mA·cm−2 at 1.23 V vs. RHE represents an 1.84-fold improvement over that of TiO2/Cu2O. Specifically, the ultrathin Al2O3 passivation layer spontaneously generated on the surface of Al in air could act as a protective layer to significantly increase its stability. In this work, the synergistic effect of the heterojunctions and the SPR effect of the non-noble metal Al significantly improve the photoelectrode performance, providing a novel concept for the design of electrodes with good properties and high practicability.