Two different polymorphs of α-ZnMoO4 and β-ZnMoO4 were successfully synthesized by simple hydrothermal method and subsequent heat treatment. The XRD, XPS, SEM and EDX techniques were used to characterize their structure and morphology. The electrochemical performances were studied. It is found that α-ZnMoO4 has more outstanding electrochemical performance than that of β-ZnMoO4. The α-ZnMoO4 has an initial discharge specific capacity of 1432.3 mAh g−1, and maintain it as 1008.7 mAh g−1 after 100 cycles at a current density of 0.2 A g−1. However, the initial capacity of β-ZnMoO4 is only 892.5 mAh g−1. It kept at 271.0 mAh g−1 after 100 cycles. At the same time, the rate performance of α-ZnMoO4 is better than that of β-ZnMoO4. Therefore α-ZnMoO4 is a promising anode material for lithium ion batteries (LIBs) application.