Some aspects concerning the chemistry of oxidative transformation of paraffins catalyzed by different classes of materials are examined. Attention is given mainly to: (i) the role of the redox properties of transition metal oxide-based systems, and (ii) the contribution of radical-type, homogeneous and heterogeneously-initiated homogeneous reactions over nonreducible metal oxide catalysts. Technological solutions aimed at the control of oxidizing properties of the catalyst are also examined.