Ce0.25V2O5(H2O)·H2O (CeVO) or Ce0.3V2O5(H2O)·H2O/S (CeVS) was synthesized based on a facile one-step hydrothermal reaction of Ce(SO4)2 and V2O5 or VS2. Rietveld refinement of CeVO unveils the intercalation of Ce ions into layered V2O5 with a large (001) lattice spacing of 12.1 Å. CeVS is a CeVO/S heterostructure, which originates from the hydrothermal transformation of VS2 → V2O5 + S8 and the simultaneous intercalation of Ce ions. The pre-intercalation of Ce ions leads to a Zn2+ migration barrier of 1.32 eV in CeVO, and CeVO shows a capacity of 376 mA h g-1 at 0.1 A g-1. However, CeVS exhibits a higher capacity (438 mA h g-1) and an ultralong lifespan with a capacity retention of 100% over 10 500 cycles at 5 A g-1. The conversion between S0 and vanadium sulfide (yS0 + 2e- ↔ Sy2-) in CeVS during the discharge and charge process can not only provide extra capacity, but also maintain the crystallinity and stability of CeVO, in which S transfers electrons like an electron shuttle to avoid the structural collapse and fast capacity fading of CeVO.