The recycling of spent batteries has always been a daunting and difficult task throughout the long history of battery development. Zinc−carbon batteries, one of history's most popular batteries, still widely used today, have become a serious environmental problem. Although zinc−carbon batteries are the first primary batteries that belong to non-rechargeable cells, they are still widely used as a result of their low cost and ease of product. Currently, thousands of tons of zinc−carbon batteries are released into the environment each year, requiring advanced recycling methods. Among various strategies that have been developed, electrochemistry is one of the interesting methods, with the advantages of being cheap and fast and able to synthesize a new material, graphene, a material that changes the technology game. Graphene derived from carbon rods in spent zinc−carbon batteries has been successfully synthesized by a short-time, simple instrumentation of electrochemical exfoliation under direct current supply, which demonstrates a low-cost and environmental strategy for mass production of graphene material from electronic device waste. This review provides a great overview aiming to introduce the electrochemical exfoliation method to recycle spent zinc−carbon batteries to synthesize graphene materials, which contributes to battery recycling technology as an alternative strategy.