Today, dyes are one of the major problematic pollutants in the environment and are broadly used in several industrial sectors. In the current research work, decolorization of safranin (basic dye) from aqueous solution was investigated using iron-impregnated peanut shell ash (Fe-PSA) as a catalyst in the UV-assisted heterogeneous Fenton process (Fe-PSA/H2O2/UV). The effect of parameters such as H2O2 concentration, catalyst dose, pH, initial dye concentration, temperature, and agitation speed was studied. The maximum decolorization of safranin was achieved at optimum parametric values of reagent dose = 8 mM, catalyst dose = 0.5 g, pH = 3, initial concentration of safranin = 50 ppm, temperature = 25 °C, and agitation speed = 200 rpm. The results revealed the efficient performance of Fe-PSA as catalyst in the Fe-PSA/H2O2/UV process for safranin treatment.