Ultrathin MoO2 nanosheets encapsulated in carbon matrix were fabricated through a facile interfacial self-assembly of laminar MoO3 nanosheets, followed by thermal reduction to MoO2 mediated by glucose. The resulting MoO2/C nanosheets exhibited a superior Li-storage capacity, retaining 1051mAhg−1 over 100 cycles at a rate of 0.5Ag−1, and 719mAhg−1 over another 100 cycles at a high rate of 5Ag−1 (based on the total mass of MoO2 and carbon). More importantly, the MoO2/C nanosheets exhibit robust rate capability, affording a stable capacity of 544mAhg−1 at an extremely high rate of 10Ag−1, thereby suggesting their great potential as promising electrode materials for high power battery applications such as electric automobiles and power tools.