The structure of copper iron pyrophosphate catalysts prepared with various atomic ratios of metals and different pretreatment conditions was studied by using XRD, FT-IR, DR UV-vis and H-2-TPR techniques. The preparation methods modify the phase composition, oxidation state and reducibility of the patterns. The catalytic properties in the selective oxidation of methane to formaldehyde and methanol were examined in both, pulse and flow reactors, using O-2 and/or N2O oxidizing agents. The oxidants used impact the onset of methane conversion, the primary oxidation products formation and the methane conversion. The highest single-pass yield of useful oxygenates (1.8%) was achieved with N2O over the Cu/Fe congruent to 1:2 pyrophosphate catalyst which consists mainly of the crystalline (FeFe2III)-Fe-II(P2O7)(2) and copper containing nanodomains. Enhanced interaction and cooperation between these phases leading to a synergic effect of Cu and Fe has been emphasized. The Cu-II and Fe-III species of the above structure can be reduced more easily but at similar temperatures than those in the crystalline CuFe2(P2O7)(2). Pulse reaction studies indicate that the lattice oxygen of the catalyst could react with methane molecules producing formaldehyde and methanol and replenishment of the lattice oxygen by N2O takes place rather readily and rapidly. The nature of active species, methane conversion and oxygenates selectivity remained almost unchanged during the time on stream. (C) 2011 Elsevier B.V. All rights reserved.