Directional and high-efficiency charge transport to the target active sites of photocatalyst is central to boost the solar energy conversion but is retarded by the sluggish charge transfer kinetics and deficiency of active sites. Here, we report the elaborate design of cascade unidirectional charge transfer channel over spatially multilayered CdS@CdTe@MoS2 dual core-shell ternary heterostructures by partial transformation of CdS to CdTe interim layer followed by seamless encapsulation with an ultrathin MoS2 layer. The suitable energy-level alignment and unique coaxial multilayered assembly mode among the building blocks accelerate the interfacial charge separation and transport, endowing the CdS@CdTe@MoS2 heterostructures with conspicuously enhanced visible-light-driven photocatalytic hydrogen generation performances along with good photostability. The integrated roles of ultrathin CdTe intermediate layer in passivating the defect sites of CdS NWs framework, mediating the unidirectional charge transfer cascade and prolonging the charge lifetime, were ascertained. Besides, the crucial role of the outermost MoS2 layer as the metal-free cocatalyst in enriching the surface active sites for hydrogen evolution was also determined. Our work would provide new alternatives for finely tuning the charge flow toward promising solar-to-hydrogen conversion efficiency.