Local structural changes in a porous NiSi2/Si composite anode material are investigated by X-ray absorption spectroscopy. It is observed that the NiSi2 phase shows a strong metal-metal bond character and no clear changes can be observed in XANES during lithiation and de-lithiation. The variation of the number of nearest neighbors of the Ni atom for the 1st coordinate Ni-Si shell and σ 2 in the 1st cycle, both determined by refinement, demonstrates that NiSi2 can partially react with lithium during discharge and charge. A partially reversible non-stoichiometric compound NiSi2−y is formed during cell operation, the crystal structure of which is the same as that of the NiSi2 phase. It can be concluded that NiSi2 in the composite not only accommodates the pronounced volume changes caused by the lithium uptake into silicon, but also contributes to the reversible capacity of the cell.