Lithium vanadium fluorophosphate (LiVPO4F) has been attracted increasing attention as an advanced cathode for Li-ion batteries because of its excellent thermal stability and high operating voltage. Nevertheless, the pure LiVPO4F possesses a low electrical conductivity which prevents its usage for practical application in energy storage. In this work, the CNTs-decorated LiVPO4F/C (CNTs@LiVPO4F/C) nanocomposite has been prepared via a conventional sol-gel approach. The XRD results reveal that all the diffraction peaks obtained for CNTs@LiVPO4F/C are indexed to the triclinic structure. TEM images show that the conductive CNTs are distributed homogeneously over the LiVPO4F/C particles. Benefiting from the enhanced conductivity, the as-prepared CNTs@LiVPO4F/C electrode exhibits outstanding electrochemical performance with high reversible capacity of 121.1 mAh g−1 at a high current rate of 10C. Therefore, the novel CNTs@LiVPO4F/C cathode material developed from this investigation with superior Li-storage performance has promising practical applications in electrochemical energy storage systems.