The kinetic and thermochemical analyses of the catalytic oxidation of C-1-C-4 alkanes indicate that the overall reaction network includes both homogeneous and heterogeneous elementary reactions of free radicals. Two thermochemical parameters of oxide catalysts, the affinity of the surface active site E[O-H] to a hydrogen atom and oxygen binding energy E-[O], are the main factors determining the kinetic features of the overall process. The possible contribution of free radical reactions to some metal-catalyzed processes (steam reforming, partial and total oxidation of methane) is analyzed. Trends in the studies of catalytic chemistry of free radicals and in the development of innovative catalytic processes of light alkane transformation into valuable products are discussed. (C) 2003 Elsevier Science (USA). All rights reserved.