For the first time Cu2O particles with different morphologies are synthesized by adopting a polyol process performed at different temperatures. SEM and TEM show that the samples obtained at 140 and 160°C present a core-shell structure. XRD measurements indicate that both samples exhibit better crystallinity compared with the samples obtained at 120°C. Results from charge–discharge experiments and cyclic voltammograms (CV) reveal that morphology and crystallinity play important roles in determining the electrochemical performance of Cu2O samples.