Semiconductor materials have shown a good photocatalytic behaviour for the photodegradation of organic pollutants. In this work, maleated liquid natural rubber (MLNR) based hydrogel supported bismuth ferrite (BiFeO3) as photocatalyst was successfully synthesized by crosslinking with acrylic acid (AAc) assisted by the ultrasonication method to study the efficiency for the removal of methylene blue (MB) dye in wastewater. Response surface methodology (RSM) was used to optimize the parameters for adsorption of the methylene blue (MB) dye compound, whereby the effects of the initial concentration of MB and the adsorption time were examined to obtain a quadratic model for the respective hydrogel composite. The prepared composite sample was characterized by Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscopy-Energy Dispersive X-ray (SEM-EDX) and X-ray Diffraction (XRD) analysis. Remarkable improvement for removal of methylene blue (99% removal) was found within 3 h adsorption time with a MLNR/AAc-BiFeO3 hydrogel composite as compared to the pristine hydrogel. A synergistic mode of dye removal by adsorption and photodegradation is proposed. Based on the isotherm and kinetic study conducted, it was found that Freundlich isotherm model and a pseudo second-order kinetic model was best fitted for adsorption of MB dye. The MLNR/AAc-BiFeO3 composite maintains its removal efficiency after 5 cycles without the necessity of post-treatment separation. Therefore, it is crucial to note that the resultant low-cost MLNR/AAc-BiFeO3 hydrogel composite in this study offers excellent potential for water and wastewater treatment applications with improved recyclability and recovery.