Nanomaterials are a promising class of ideal high performance candidates for photocatalytic application owing to their unique optical, structural and electronic properties. In this respect, silicon carbide (SiC) has proven to be technologically important material. The occurrence of different polytypes of SiC along with their individual characteristic electrical, chemical and thermal properties made it suitable for photocatalytic material for hydrogen generation and environmental remediation. Here we demonstrate the significant effect of surface modification in enhancement of photocatalytic activity of SiC. The confinement effects of the different polytypes of crystalline SiC and amorphous SiC are also being addressed. Graphitization of SiC by high temperature thermal decomposition method has been employed to grow epitaxial graphene (EG) on silicon carbide (EG/SiC hybrid system) to design the surface and interface structure in controlled manner. The systems have been characterized by Raman and UV-vis spectroscopies along with the XRD, SEM and HRTEM analysis. Significant enhancement of the photocatalytic activity (~1000%) and bandgap narrowing (~30%) of EG/SiC systems were observed, relative to the bare SiC, depending on the quality and quantity of the EG and heterojunction interface structures. The effect of different types of SiC (crystalline and amorphous) at their different confinement levels (thin films, nanoparticles) have been studied further to explore the potential application in photocatalysis for renewable energy and environmental remediation (e.g., waste water treatment).