The present work focuses on synthesizing graphene nanoplatelets (GNP) incorporated amorphous silicon oxycarbide ceramic (Si-O-C) for hydrogen adsorption. The changes in the structure of the ceramic upon addition of GNP has been studied using X-ray diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS), Raman Spectroscopy and Fourier Transform Infrared (FT-IR) spectroscopy. A theoretical framework to quantify these changes is proposed in line with existing structural model. Hydrogen adsorption studies have been carried out at 100K and 2 bar using Sievert’s apparatus. Maximum gravimetric storage density (GD) of 0.16 wt.% was observed after adding 0.3 wt.% of GNP, in comparison to 0.35 wt.% for the non-GNP sample. Pores sized 2–5 nm were found to be critical for hydrogen adsorption. The study finds that GNP addition leads to an increase in the size of the silica nanodomains. This increase in nanodomain size results in increase in the pore sizes of the existing mesopores, thereby reducing the overall hydrogen uptake. Further, the addition of GNP beyond 3 wt.% is found to increase the coordination of mixed bonds (Si-O-C) in the interface which results in agglomeration and subsequent loss of porosity in the composite.