Cubic and star-shaped CaSnO3 particles with a perovskite structure were synthesized successfully using a simple hydrothermal method at a low temperature of 140 °C. The structure and morphology of the CaSnO3 powders were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The electrochemical properties of the CaSnO3 as anode materials for lithium-ion batteries were tested by constant current discharge/charge and cyclic voltammetry. The large irreversible capacity in the initial cycle was similar to that of tin oxide, due to the decomposition of tin oxide into metallic tin and Li2O, followed by a reversible Li–Sn formation. The reversible capacity of the cubic CaSnO3 was 382 mAh g−1 in the first cycle and was maintained at 365 mAh g−1 in the following cycles. The cubic CaSnO3 particles had a higher reversible capacity than the star-shaped CaSnO3 particles and retained a capacity of about 365 mAh g−1 after 60 cycles as well as good cycle stability, showing potential as attractive anode materials for lithium-ion batteries. It is found that the particle shape had a marked effect on electrochemical performance.