Lithium vanadium fluorophosphate (LiVPO4F) composite with three-dimensional conductive networks architecture is synthesized with synergistic modification of pyrolytic carbon (C), multi-walled carbon nanotubes (MWCNTs) and graphene sheets (rGO). The differences between LiVPO4F@C, LiVPO4F@C/MWCNTs, LiVPO4F@C/rGO and LiVPO4F@C/MWCNTs/rGO composites are compared through a variety of characterization means. By means of SEM and TEM analysis, it can be seen that pyrolyzed C, MWCNTs and rGO are interwoven, which forms a three-dimensional conductive network structure wrapping the LiVPO4F particles. The difference of discharge specific capacity between LiVPO4F@C and LiVPO4F@C/MWCNTs/rGO composites is becoming larger and larger with the increase of charge-discharge rate. Additionally, CV and EIS results indicate that the LiVPO4F@C/MWCNTs/rGO has the smallest polarization value and charge transfer impedance (Rct) as well as the highest diffusion coefficient of lithium ion (DLi+) in all samples. Consequently, LiVPO4F@C/MWCNTs/rGO composite exhibits a high rate capability (97.9 mAh/g cycles at 10 C) and cycling stability (93.74% capacity retention over 800 cycles at 10 C)，showing potential application for high power LIB with high voltage.