MoS₂ has attracted great attentions due to the high capacity and layered crystal structure. Whereas the intrinsic poor conductivity and big volume change of common used 2H-MoS₂ bring about poor rate capability and bad cycling performance. Herein, three-dimensional N, P co-doped carbon network modified mixed phases of 1T/2H-MoS₂ heterostructures (1T/2H-MoS₂@PNC) have been rationally fabricated through a facile three-step strategy. Dependent on the cooperate effect of 1T/2H-MoS₂ heterostructure and N, P co-doped carbon network, the 1T/2H-MoS₂@PNC exhibits a high reversible capacity (475 mAh g⁻¹ at 0.5 A g⁻¹), outstanding rate capability (347 mAh g⁻¹ at 10 A g⁻¹) and long-term cyclic life up to 1000 cycles without capacity loss, obviously superior to 1T/2H-MoS₂@PNC with different carbon contents/synthesis temperatures, 2H-MoS₂@PNC and 1T/2H-MoS₂@NC. Reaction kinetics and theoretical calculation have been investigated to verify the synergetic advantages of 1T/2H-MoS₂ and N, P co-doping of carbon networks. Moreover, various ex-situ techniques have been employed to disclose the reaction mechanism of 1T/2H-MoS₂@PNC. The assembled Na₃V₂(PO₄)₃//1T/2H-MoS₂@PNC full batteries also demonstrate good electrochemical properties (a discharge capacity of 216 mAh g⁻¹ over 300 cycles at 0.5 A g⁻¹). All the results manifest the prospective application of 1T/2H-MoS₂@PNC as high-performance anode materials for large-scale energy storage.