A series of hollow structured (Sn,Ti)O2 solid-solutions with varying Sn content are prepared by a soft template method. Not only a complete incorporation of Sn4+ into TiO2 lattice but also a SnOTi bonding is identified, and morphologically, interconnected pores are confirmed between the hollow (Sn,Ti)O2 solid-solution nanoparticles. In battery performance, along with enhanced lithium storage, consistent utilization of Sn in voluminous alloying/de-alloying reactions is demonstrated. Beyond the TiO2 typically known as a stable anode material, the superior capacity retention of solid-solution rather containing Sn shows that the SnOTi bonding in (Sn,Ti)O2 solid-solution leads to the synergy effect of increased energy density from Sn and stable capacity retention from Ti.