A simple, green and cost-effective approach has been reported to synthesize high-quality graphene oxide (GO) flakes via electrochemical exfoliation of pencil cores in aqueous electrolytes. The exfoliated GO flakes exhibit excellent electrocatalytic activity and toxicity tolerance for oxygen reduction reactions in alkaline solution. Our present results are promising for scaled-up preparation and further commercialization of graphene oxide in a low-cost and environmentally friendly way.