Through facile one step sol-gel method, Li2MnSiO4-based cathode materials have been successfully synthesized and co-modified with carbon and MoO2 coating. The phase compositions and morphology of the as-prepared products have been characterized by XRD, SEM and TEM. The physical characterization indicates the introduced MoO2 exists on the particle surface of orthorhombic Li2MnSiO4, forming a hybrid coating layer with amorphous carbon. Meanwhile, the addition of MoO2 improves the dispersion of particle size distribution. Therefore, the electrochemical performance of the pristine Li2MnSiO4/C has been significantly improved after coating MoO2, especially in the case of 1wt% MoO2 component. The optimal as-prepared sample exhibits a reversible capacity of 184.9mAh/g at 0.1C and maintains 127.5mAh/g even at a high rate of 1C. The excellent rate performance can be attributed to reduced interfacial resistance and enhanced lithium ion diffusion coefficient.