We report the synthesis of a novel branched nano-heterostructure composed of SnO2 nanowire stem and α-Fe2O3 nanorod branches by combining a vapour transport deposition and a facile hydrothermal method. The epitaxial relationship between the branch and stem is investigated by high resolution transmission electron microscopy (HRTEM). The SnO2 nanowire is determined to grow along the  direction, enclosed by four side surfaces. The results indicate that distinct crystallographic planes of SnO2 stem can induce different preferential growth directions of secondary nanorod branches, leading to six-fold symmetry rather than four-fold symmetry. Moreover, as a proof-of-concept demonstration of the function, such α-Fe2O3/SnO2 composite material is used as a lithium-ion batteries (LIBs) anode material. Low initial irreversible loss and high reversible capacity are demonstrated, in comparison to both single components. The synergetic effect exerted by SnO2 and α-Fe2O3 as well as the unique branched structure are probably responsible for the enhanced performance.