Nitrogen-doped graphene quantum dots (NGQDs) are a diverse organic catalyst, competitive with other metallic catalysts due to their low cost, high stability, biocompatibility, and eco-friendliness. Highly functional multi-edge surfaces of NGQDs play a key role in imparting superb photocatalytic and electrocatalytic activity. However, when coating NGQDs by conventional techniques, such surfaces are not exposed for catalysis, due to the unwanted overlap of NGQDs sheets. To avoid this issue, here we propose a facile technique to orient NGQDs in a three-dimensional (3D) self-assembled foam-like structure, over reduced graphene oxide coated woven carbon fabric. This 3D assembled structure provides highly exposed active surfaces, which are readily available for catalytic reactions: however, in the conventional uniformly coated NGQDs layer, catalytic activity was limited by complex diffusion. The superb catalytic activity of the assembled NGQDs was utilized for the degradation of organic pollutant (methylene blue dye) from water. Additionally, the proposed electrode revealed much higher electrocatalytic activity than the rare Pt catalyst, owing to the easy diffusion of electrolyte and fast quenching of charges through the porous structure. The assembled NGQDs showed 50% higher photocatalytic degradation compared to uniformly coated NGQDs, which was further accelerated (50%) by application of the biased potential of 2 V; i.e. photo-electrocatalysis. The novel photo-electrocatalytic electrode offers high conductivity, stability, and flexibility, which make this complete carbon electrode highly attractive for other catalytic applications such as fuel cells, supercapacitors, and water splitting. (C) 2019 Published by Elsevier Inc.