The vacuum deposition method requires high energy and temperature. Hydrophobic reduced graphene oxide (rGO) can be obtained by plasma-enhanced chemical vapor deposition under atmospheric pressure, which shows the hydrophobic surface property. Further, to compare the effect of hydrophobic and the hydrophilic nature of catalysts in the photoelectrochemical cell (PEC), the prepared rGO was additionally treated with plasma that attaches oxygen functional groups effectively to obtain hydrophilic graphene oxide (GO). The hydrogen evolution reaction (HER) electrocatalytic activity of the hydrophobic rGO and hydrophilic GO deposited on the p-type Si wafer was analyzed. Herein, we have proposed a facile way to directly deposit the surface property engineered GO.