The synthesis of graphene in both high quality and quantity via economic ways is highly desirable and meaningful for practical applications. Here we report a simple, green and cost- effective multiple electrochemical exfoliation approach to high quality and high yield (nearly 50%) graphene flakes by using graphite rod from spent zinc–carbon as graphene source. The graphite rod (anode) and platinum (cathode) were placed vertically at bottom and top of the electrochemical cell, with protonic acid (i.e, H2SO4, H3PO4 or H2C2O4) aqueous solution as electrolyte. The vertical cell configuration enables multiple exfoliation process to improve both the quality and yield of graphene sheets from electrochemical exfoliation of graphite. After nitrogen doping, the exfoliated graphene flakes processes excellent electrocatalytic activity, stability and toxicity tolerance for oxygen reduction reaction in alkaline solution.