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• Photocatalyst Water splitting as clear energy for hydrogen evolution reaction. • Silicon earth-abound material as substrate photoabsorber absorbs wide range solar light. • Carbon material low cost, high chemical stability for water splitting. • Graphene synthesis by different methods, next though to transferred to silicon by polymer substrate as a catalyst layer. In the present report, graphene-based catalysts on silicon substrate have been examined as the photocathode for solar hydrogen evolution reaction (HER). Mono-layered graphene has been synthesized through low-pressure chemical vapor deposition (LPCVD), whereas multi-layered graphene has been synthesized by atmospheric pressure chemical vapor deposition (APCVD). Copper foil is used as the substrate. The graphene layer on Cu foil subsequently transferred on to silicon photoabsorber using poly(methyl-2-methylpropenoate) (PMMA). At the initial linear sweep voltammetry (LSV) scan, LPCVD-synthesized graphene-Si (LPCVD-Si) electrode showed an onset potential of −0.65 V and photocurrent of −4.31 mA cm−2 (at −0.385 V). On the contrary, the onset potential and photocurrent of APCVD-prepared graphene-Si (APCVD-Si) photocathode are −0.36 V and −28.28 mA cm−2 (at −0.385 V), respectively. After the 130th LSV scan, the onset potential and photocurrent of LPCVD-Si improved to −0.39 V and −13.28 mA cm−2 (at −0.385 V), respectively. In addition, the onset potential and photocurrent of APCVD-Si photocathode at the LSV 130th scan are enhanced to −0.36 V and −28.28 mA cm−2 (at −0.385 V), respectively. The graphene sample grown via LPCVD-Si show stable performance whereas, the graphene obtained via APCVD-Si have higher photocurrent poor stability. [ABSTRACT FROM AUTHOR]