Recent development of electrode materials for Li-ion batteries is driven mainly by hybrid nanocomposite structures consisting of Li storage compounds and CNTs. In this study, tin/tinoxide (Sn/SnO2) films and tin/tinoxide/multi walled carbon nanotube (Sn/SnO2/MWCNT) nanocomposites are produced by a two steps process; thermal evaporation and subsequent plasma oxidation as anode materials for Li-ion batteries. The physical, structural, and electrochemical behaviors of the nanocomposite electrodes containing MWCNTs are discussed. The ratio between metallic tin (Sn) and tinoxide (SnO2) is controlled with plasma oxidation time and effects of the ratio are investigated on the structural and electrochemical properties. The greatly enhanced electrochemical performance is mainly due to the morphological stability and reduced diffusion resistance, which are induced by MWCNT core and deposited Sn/SnO2 double phase shell. The outstanding long-term cycling stability is a result of the two layers Sn and SnO2 phases on MWCNTs. The nanoscale Sn/SnO2/MWCNT network provides good electrical conductivity, and the creation of open spaces that buffer a large volume change during the Li-alloying/de-alloying reaction.