A series of copper on silica catalysts prepared by using the ion exchange methods with copper loading between 0.45 and 3 wt% have been studied by means of different techniques such as TPR, EPR, XANES, XRD, XRF, BET and methanol dehydrogenation reaction. The TPR patterns showed two well-defined peaks with maxima between 250–350°C and 600–650°C. The first one (peak I) corresponds to two contributions: (i) the one step reduction (Cu 2+ to Cu 0) of a low interacted species (S 1), and (ii) the partial reduction (Cu 2+ to Cu 1+) of a highly dispersed and surface interacted species (S 2). The second TPR peak (peak II) observed at a higher temperature corresponds to the second step reduction (Cu 1+ to Cu 0) of the S 2 species. In addition, it has been found out that Cu 0 and not Cu 2+ is the active site for methanol dehydrogenation to methyl formate.