A new anode consisting of BaHPO4/SrHPO4 (SrP/BaP) micro-structured materials has been fabricated through two-step electrodeposition technique. Structural, vibrational, morphological, and optical properties of the anode films were investigated employing X-ray diffraction, Raman spectroscopy, scanning electron microscopy (SEM) and UV–Vis absorption spectroscopy, respectively. Photoluminescence (PL), and photo-electrocatalytic (PEC) activities of the samples were investigated and compared with those of the pure BaHPO4 (BaP) and SrHPO4 (SrP) samples. The PEC performance was of the order of 71% within 25 min, which was less than both BaP (99%) and SrP (92%) in the same experimental conditions. These results reveal that BaP thin films combined with SrP microstructures remarkably changed the PL signals, and in turn significantly enhanced the PL activities, while the PEC has been lowered down. This was attributed to the photo-induced electron–hole pairs recombination as electrochemical impedance spectrum and photo-current response have shown. Based on these results, it is believed that the SrP/BaP film behaves as a sensitizer in the system and not as a photo-electrocatalyst.