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In this study, optimizing caffeine concentrations (2%, 4%, 6%, and 8%) in MAPbI3 using a graphite electrode under acidic conditions, analysing both electrocatalytic (EC) and photoelectrocatalytic (PEC) processes was investigated. The catalyst made from Graphite and MAPbI3 with 2% caffeine shows superior performance compared to the other catalysts, particularly in the dynamic electrocatalytic process. Notably, the Graphite + MAPbI3@Caffeine 2% catalyst exhibits a significantly reduced charge transfer resistance of 9.27 ꭥ, outperforming the other catalysts we examined. Our results also indicate that the Graphite + MAPbI3@Caffeine 4% loading demonstrates exceptional stability, surpassing the stability of other catalysts. Remarkably, the double-layer capacitance (Cdl) value for the Graphite + MAPbI3@Caffeine 2% electrode is 0.00281 F/cm², which indicates a significant enhancement under PEC conditions compared to EC settings, with an effective catalyst surface area (ECSA) of 150 cm². Additionally, the turnover frequency (TOF) for the Graphite + MAPbI3@Caffeine 2% catalyst was calculated to be an impressive 348.29 s⁻¹, exceeding the performance of other electrodes within the EC process.