Phosphorus (Pi) and cadmium (Cd) contamination in water sources pose significant health risks and environmental concerns. Periphytic biofilms have been recognized for their ability to effectively remove these contaminants from aquatic environments. This study aimed to investigate the impact of photon and electron treatments on Pi and Cd removal by periphytic biofilms. The experiments spanned a monthly timeframe, focusing on how photon and electron treatments affected the contaminant removal efficiency of periphytic biofilms. The results revealed that while the introduction of electrons had a minimal impact on contaminant accumulation, the enhancement of photon exposure significantly improved the absorption capacity of periphytic biofilms. This, in turn, led to enhanced removal of Pi and Cd from the water. One possible explanation for this phenomenon is that photons played a crucial role in inducing nitrate and ammonium conversion, thereby facilitating the accumulation of 4.70 mg kg−1 Pi and 2.40 mg kg−1 Cd in periphytic biofilms. In contrast, electron treatment had limited effects on nitrate conversion. These findings provide valuable insights into the mechanisms underlying the removal of water contaminants by periphytic biofilms under the influence of electron and photon treatments. Furthermore, they have practical implications for improving pollutant removal capabilities in aquatic ecosystems using periphytic biofilms.