Abstract: The invention relates to the use of cobaloximes and related cobalt(II) complexes which have essentially planar equatorially coordinated ligands and a pair of axially coordinated ligands which have at least one carbon-cobalt bond, as photoinitiators for free radical polymerizations. By selection of the appropriate cobaloximes and related complexes, it is possible to prepare polymers which have useful terminal functionality at both the head and the tail ends of the growing polymer chain. The process also teaches the photochemical polymerization and copolymerizations whereby the alkyl cobaloximes and related compounds, which are used as the photoinitiators, have alkyl groups, which may in essence, be polymers with carbon-cobalt chain ends, thereby allowing grafting reactions to occur to the polymer backbone.