A novel mesoporous-nanotube hybrid composite, namely mesoporous tin dioxide (SnO2) overlaying on the surface of multi-walled carbon nanotubes (MWCNTs), was prepared by a simple method that included in situ growth of mesoporous SnO2 on the surface of MWCNTs through hydrothermal method utilizing Cetyltrimethylammonium bromide (CTAB) as structure-directing agents. Nitrogen adsorption-desorption, X-ray diffraction and transmission electron microscopy analysis techniques were used to characterize the samples. It was observed that a thin layer tetragonal SnO2 with a disordered porous was embedded on the surface of MWCNTs, which resulted in the formation of a novel mesoporous-nanotube hybrid composite. On the base of TEM analysis of products from controlled experiment, a possible mechanism was proposed to explain the formation of the mesoporous-nanotube structure. The electrochemical properties of the samples as anode materials for lithium batteries were studied by cyclic voltammograms and Galvanostatic method. Results showed that the mesoporous-tube hybrid composites displayed higher capacity and better cycle performance in comparison with the mesoporous tin dioxide. It was concluded that such a large improvement of electrochemical performance within the hybrid composites may in general be related to mesoporous-tube structure that possess properties such as one-dimensional hollow structure, high-strength with flexibility, excellent electric conductivity and large surface area.