The effectiveness of photocatalytic processes is dictated largely by plasmonic materials with the capability to enhance light absorption as well as the energy conversion efficiency. Herein, we demonstrate how to improve the plasmonic photocatalytic properties of TiO2/Al nano-void arrays by overlapping the localized surface plasmon resonance (LSPR) modes with the TiO2 band gap. The plasmonic TiO2/Al arrays exhibit superior photocatalytic activity boasting an enhancement of 7.2 folds. The underlying mechanisms concerning the radiative energy transfer and interface energy transfer processes are discussed. Both processes occur at the TiO2/Al interface and their contributions to photocatalysis are evaluated. The results are important to the optimization of aluminum plasmonic materials in photocatalytic applications.