RGO-alpha-Fe2O3/beta-FeOOH ternary heterostructure composite has been developed as an active photocatalyst for photoelectrochemical water splitting. RGO-alpha-Fe2O3/beta-FeOOH has been successfully synthesized through one-pot hydrothermal-ionic liquid assisted route using tetrabutyl ammonium L-methioninate [TBA][L-Met] and graphene oxide (GO). The electrochemical studies were carried out to demonstrate the oxygen evolution reaction (OER) and photocatalytic activities. The overpotential reduction by rGO-alpha-Fe2O3/beta-FeOOH sample was higher than the nanobean alpha-Fe2O3/beta-FeOOH and pristine alpha-Fe2O3 samples. The photocurrent density enhanced for rGO-alpha-Fe2O3/beta-FeOOH urchin-like structure and obtained as 0.62 mA.cm(-2). The data evidences the idea that the beta-FeOOH layer in the modified morphology acts as an electron donor and the donor density increased substantially. Results from this study indicate that the rGO-alpha-Fe2O3/beta-FeOOH can improve OER performance significantly with a peak shift of 0.13 V in the potential window, revealing its excellent potential as a higher rate and lower energy needed candidate.