We prepared nano-sized tin (IV) oxide (SnO2) via molten-salt technique: heating a mixture of tin tetrachloride, lithium nitrate and lithium chloride at 280°C in air. The powders are characterized by X-ray diffraction and transmission scanning microscopy techniques. The XRD studies showed a structure similar to tetragonal structure. The cyclic voltammetry studies showed characteristic cathodic peak potentials of reduction of Sn4+ to Sn metal in the first cathodic scan, and alloying–de–alloying reaction of Sn at ∼0.25 and ∼0.5V vs. Li for successive cathodic and anodic scans cycled in the voltage range, 0.005–1.0V. Galvanostatic cycling studies show that reversible capacities (MSM SnO2 prepared at 280°C) of 640, 720, 890mAhg−1 in the voltage range, 0.005–1.0V, 0.005–1.3V and 0.005–1.5V, respectively at a current rate of 100mAg−1. We also discussed the effect of particle size and its electrochemical properties in the voltage range, 0.005–1.0V.