Heterostructures have broad potential application in energy conversion material and optoelectronic device since of novel interface effect and enhanced electron transport dynamics at heterointerfaces. Herein, we report a heterostructured SnS/SnO2/spherical graphene composite, in which ultrafine SnS/SnO2 nanoparticles with heterostructures are sandwiched between multi-layers of graphene sheets, exhibiting a hollow spherical architecture as a whole. Detailed electrochemical studies indicate that the molar ratio of SnS to SnO2 has great influence on the charge transport efficiency. Theoretical calculation reveals that SnS and SnO2 exhibit different work functions and the Fermi level shift is affected by the SnS/SnO2 molar ratio, thus the hybrid with the ratio close to 1.0 owns the most adsorbed lithium ions, which leads to the highest specific charge-transfer kinetics and lowest ion-diffusion resistance than other samples. Electrochemical tests show that the composite with appropriate composition delivers the best lithium storage rate performance (620 and 312.7 mAh g−1 at 1 C and 10 C). A much stable and high reversible specific capacity of 850 mAh g−1 is obtained after 200 cycles at 0.1 C. The appropriate molar ratio of nano-heterostructures and the novel sandwich hollow spherical composite structure are attributed to the excellent electrochemical performances.