Sn-based materials have motivated tremendous interest owing to their fascinating theoretical capacity in lithium-ion batteries. Nevertheless, the complex synthesis process and the use of toxic solvents hinder the sustainable development of Sn-based materials. Herein, we propose a simple strategy for the controllable synthesis of Sn-based materials, including Sn/SnO/mesoporous carbon (MC), Sn/SnO/SnO2/MC composites and SnO2 nanoparticles. The three-phase composites (Sn/SnO/MC) comprise dispersed Sn particles, a small amount of SnO nanosheets, and the carbonaceous matrix MC. Due to the loose binding between Sn (SnO) and carbon matrix as well as the severe agglomeration of SnO2 nanoparticles, the obtained Sn/SnO/SnO2/MC and pure SnO2 anodes display inferior electrochemical properties to Sn/SnO/MC. Specifically, the Sn/SnO/MC composite delivers a superior discharge capacity (670.3 mAh/g after 100 cycles) and impressive long-term cyclability (457.2 mAh/g after 450 cycles). In-situ XRD measurement is executed to analyze the phase evolution process of the Sn/SnO/MC anode. Moreover, the cycled full cell can lighten the “DMU” pattern composing 34 LEDs. It is significantly momentous and valuable to controllably synthesize high-performance Sn-based anode materials via a simple strategy.