Ni0.5TiOPO4 oxyphosphate exhibits good electrochemical properties as an anode material in lithium ion batteries but suffers from its low conductivity. We present here the electrochemical performances of the synthesized Ni0.5TiOPO4/carbon composite by using sucrose as the carbon source. X-ray diffraction study confirms that this phosphate crystallizes in the monoclinic system (S.G. P21/c). The use of the Ni0.5TiOPO4/C composite in lithium batteries shows enhanced electrochemical performances compared with the uncoated material. Capacities up to 200mAhg−1 could be reached during cycling of this electrode. Furthermore, an acceptable rate capability was obtained with very low capacity fading even at 0.5C rate. Nevertheless, a considerable irreversible capacity was evidenced during the first discharge. In situ synchrotron X-ray radiation was utilized to study the structural change during the first discharge in order to evidence the origin of this irreversible capacity. Lithium insertion during the first discharge induces an amorphization of the crystal structure of the parent material accompanied by an irreversible formation of a new phase.