This thesis focuses on the synthesis and characterization of various carbon allotropes (e.g., graphene oxide/graphene, graphene foam (GF), GF/carbon nanotube (CNT) hybrids) and their composites for electrochemical energy storage applications. The coverage ranges from materials synthesis to electrochemical analysis, to state-of-the-art electrochemical energy storage devices, and demonstrates how electrochemical characterization techniques can be integrated and applied in the active materials selection and nanostructure design process. Readers will also discover the latest findings on graphene-based electrochemical energy storage devices including asymmetric supercapacitors, lithium ion batteries and flexible Ni/Fe batteries. Given the unique experimental procedures and methods, the systematic electrochemical analysis, and the creative flexible energy storage device design presented, the thesis offers a valuable reference guide for researchers and newcomers to the field of carbon-based electrochemical energy storage.