To overcome the issue of inferior cycling stability and rate capacity for SnO2 anode materials in lithium-ion batteries, an effective strategy is explored to prepare a hybrid material consisting of rutile SnO2 nanoparticles and rutile TiO2 nanorods, considering not only the small lattice mismatch to achieve a better composited lattice structure but also their superior synergistic effect in electrochemical performances. The as-prepared SnO2@TiO2 material, directly formed on a carbon cloth as a binder-free anode, exhibits a reversible capacity of 700 mAh g−1 after 100 discharge/charge cycles at 200 mA g−1, as well as excellent cycling stability and rate capacity. After being calcinated at high temperature, the produced hollow SnO2@TiO2 hybrid microtubes were directly used to fabricate photoelectrochemical (PEC) UV detectors for future devices with self-powered function. A high photocurrent response of 0.1 mA cm−2 was observed, together with an excellent self-powered and fast response and “visible blind” characteristics. Such a hybrid material could achieve a complementary effect in lithium-ion batteries and a superior band gap match in photovoltaic devices, and could consequently be extended to applications such as dye-sensitized solar cells and supercapacitors.