 Industrial scale manufacturing with tunable properties of graphene nano-sheets has been a practical concern in many applications. This study focuses on, a physical electro-chemistry approach for the synthesis of few-layer graphene nano-sheets (FLGNSs) in a scalable manner. The intercalates are bias-driven anions towards the working electrode of bulk pyrolytic graphite sheet followed by their exfoliations as FLGNSs. In-situ electrochemical studies confirm a higher rate of exfoliation with an increase in the concentration of intercalates. Based on colloidal conductivity and particle size analyses, the degree of crystallinity and effect of variation in intercalates is explored. Rate of oxidation, defects, morphological variation, and number of layers with variation of intercalate concentration have been studied by XRD, Raman spectroscopy, FTIR, UV–Vis spectroscopy, XPS, and electron microscope based analyses. Cost-effectiveness of the electrochemical process in producing FLGNSs is assessed by considering cost of raw materials used in this laboratory process.