The selective oxidation of methane to formaldehyde has been investigated over a series of Zr-Mo-oxide catalysts. Comparative characterization of these catalysts has been carried out by BET specific surface area (BET), X-ray diffraction (XRD), laser Raman spectroscopy (LRS), temperature programmed reduction of hydrogen (H-2-TPR), and X-ray photoelectron spectroscopy (XPS). The Zr-Mo-oxide catalyst with 12 wt% Mo is found to be highly selective and yields formaldehyde by selective oxidation of methane. The interaction between Mo and Zr induces changes of physicochemical properties such as structure, crystal size, reducible properties, charge of ion and molybdenum oxide species etc., which in turn determines the catalytic performance. These effects are a function of Mo content. Zr(MoO4)(2) in these catalysts might be responsible for selective oxidation of methane to formaldehyde.