Since its first exfoliation in 2004, graphene has been extensively studied in many areas of material engineering due to its attractive properties. Graphene-based hybrid materials (GHMs) combined with advantageous materials, such as graphene, have shown broad application prospects in the fields of electronics, optoelectronics, energy storage, and conversion. High-efficiency and low-cost industrial scale methods must be developed to produce high-quality GHMs and realize their potential applications. Electrochemical exfoliation is one of the most promising methods for GHMs production because of its mild operating conditions, short time, and simple instruments. In this review, we briefly introduce electrochemically prepared graphene on the basis of their differences in exfoliation electrodes and then review the electrochemical exfoliation of GHMs. Factors affecting the hybridization of graphene, the possible hybrid mechanism, and the potential application prospects are also elucidated. Lastly, insights and perspectives on current research challenges and future opportunities regarding the electrochemical exfoliation and applications of graphene and its hybrids are discussed.