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CaMoO4 nanoparticles/graphene oxide (CaMoO4/GO) composites are prepared by a facile hydrothermal method. CaMoO4 nanoparticles are adsorbed on the GO sheets by in situ reduction. Along with the synergistic effect between the CaMoO4 and GO sheets, the CaMoO4/GO nanocomposites exhibited high performances as electrodes for supercapacitors. The specific capacity (Qs) of the CaMoO4/GO electrodes could be up to 571.82F⋅g−1 at 0.5A⋅g−1. Furthermore, asymmetric supercapacitors (ASCs) are mainly composed of CaMoO4/GO composite and activated carbon (AC), respectively. The fabricated CaMoO4/GO//AC devices display an energy density of 25.18W⋅h⋅kg−1 at 1710.3W⋅kg−1. A blue LED is powered using two series-connected two ASC devices. These results indicate the considerable potential of CaMoO4/GO for use in high-performance energy storage devices.