A new nano-sized polymer-supported Schiff base–cobalt complex catalyst based on crosslinked polyacrylamide was synthesized and characterized. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) of the catalyst show nanosize fiber-like image of the polymeric catalyst. The catalyst activity was studied in the oxidation of various olefins including non-activated terminal olefin in water with hydrogen peroxide as an oxygen source. The catalyst showed high degree of selectivity. The effects of reaction parameters such as solvent, oxidant, temperature, molar ratio of catalyst and catalyst structure on the oxidation of styrene were investigated. The oxidation of benzyl halides to their corresponding carbonyl compounds in the presence of this heterogeneous catalyst was studied as well. The catalyst can be recycled several times without significant loss in its activity.