Nitrogen-doped graphene quantum dots (N-GQDs) are emerging electroactive and visible light active organic photocatalysts, known for their high stability, catalytic activity and biocompatibility. The edge surfaces of N-GQDs are highly active, however, when N-GQDs make the film the edges are not fully exposed for catalysis. To avoid this issue, the N-GQDs are shaped to branched leaf shape, with an extended network of voids, offering highly active surfaces (edge) exposed for electrocatalytic and photocatalytic activity. The nitrogen doping causes a decrease in the bandgap of N-GQDs, thus enabling them to be superb visible light photocatalyst, for degradation of Methylene blue dye from water. Photoluminescence results confirmed that by a synergistic combination of the highly conductive substrate; Carbon fabric coated graphene sheets (CF-rGO) the recombination of photogenerated excitons is significantly suppressed, hence enabling their efficient utilization for catalysis. Comparatively, uniformly coated N-GQDs showed 49.3% lower photocatalytic activity, owing to their hidden active sites. The degradation was further boosted by 30% by combining the electrocatalytic activity, i.e. electro-photocatalysis of the proposed electrode. The proposed electrode material was analyzed using TEM, FE-SEM, FTIR, AFM, and WA-XRD, whereas the stability of electrode was confirmed by TGA, tensile test, bending test, and in harsh chemical environments. The proposed photo-electrocatalyst electrode is binder-free, stable, flexible and highly conductive, which makes the electrode quite suitable for flexible catalytic devices like flexible solar cells and wearable supercapacitors.