The effect of the addition of lithium cations to VPO phases on the catalytic activity of methane selective oxidation is reported. Two different methods of Li+ addition were used : redox intercalation and co-precipitation. The redox intercalation procedure led to the most active promoted catalyst. XRD, FTIR, XPS characterization, oxygen isotopic exchange experiments and catalytic activity measurements using double-bed configuration were carried out. It is proposed that VPO activates methane forming of the intermediates which are further selectively oxidized by the Li+ species and that the intercalation method allows the Li+ to be well dispersed in the VPO surface and not covering completely the surface of the catalyst.