Graphene is a single layer of carbon atoms in a closely packed honeycomb lattice. As a new class of two-dimensional nanomaterial, graphene has attracted considerable attention in terms of both the experimental and theoretical aspects in recent years. The unique nanostructure and its other properties endow graphene with potential applications such as capacitors, cell images, sensors, devices, drug delivery, and solar cells. This review presents a general description of preparation route for graphene and its composites in the last few years. The new developments and improvements in its electrochemical applications in inorganic analysis, organic analysis, immunoassay and other electrochemical fields are also discussed.