Graphene, one kind of emerging carbon nanomaterial, has attracted increasing attention recently. Due to its fascinating physical and electrochemical properties, graphene as a promising electrode material has been widely used in electrochemical sensing applications. In this review, different approaches for the fabrication of graphene and the preparation of graphene-modified electrodes for electrochemical sensors are introduced. Moreover, recent research results on different graphene-based materials as an electrochemical platform for the detection of various biomolecules and chemicals are reviewed and compared. More electrochemical studies on this novel material should show up in the near future.