This study investigates the solar photo-Fenton based decolorization of a cationic dye methylene blue (MB) at circumneutral pH conditions. Water-soluble Fe(III)-citrate complex was used as a source of Fe(II) during the reaction by ligand-to-metal charge transfer under solar irradiation, and consequently, for the production of hydroxyl radicals. Solar decolorization of methylene blue was studied in sunny as well as cloudy weather, and further optimized using response surface methodology and Box-Behnken statistical experimental design. In this model, Fe(III) dose, citrate ion dose, and initial pH of the solution were used as independent parameters, and percentage decolorization of MB was used as a response. Better decolorization of MB was observed in sunny weather as compared to cloudy weather. A particular combination of parameters, i.e. pH of 7, Fe(III) of 0.5 mM, and citrate ion concentration of 10 mM, was found to achieve 89.19% and 51.22% decolorization in sunny and in cloudy weather respectively, which were the optimum/near-optimum performances for these weather conditions. Hence the process initiated with these parameters may potentially achieve better performance than any other parameter combination in all weathers, although the absolute removal would still depend on incident solar irradiation.