As a promising high capacity anode material for lithium ion batteries, the lithium insertion performance and possible insertion mechanism of binary alloy of NiSi2 were discussed. The initial lithium insertion of crystal NiSi2 can reach up to 600 mAh·g-1 , but large irreversible capacity occurrs simultaneously for serious structure transformation and the irreversible phase forms. XRD and XPS were employed to detect the crystal structure and composition changes produced by lithium insertion. The lithium insertion-extraction behavior of NiSi2 electrode is similar to that of silicon after the first discharge. The structure stability seems related to the non-stoichimometric Ni-Si compound formed by lithium insertion into NiSi2.