Poly(4-vinylpyridine-co-divinylbenzene)-Co2+ was characterized using infrared spectroscopy (IR), thermogravimetric analysis (TG-DTA), N2-physisorption and polarography. Thermal analysis suggests sufficient thermal stability of the polymer support, under reaction conditions. From polarography measurements, the Co2+ content on polymer-supported catalysts is estimated and it was proved that no significant leaching occurred during the activity tests. At the molecular level, FTIR of P4VP-DVB-Co2+ reveals that the pyridine nitrogen lone pair coordinates to the metal center in the polymeric complex. The obtained P4VP-DVB-Co2+ catalysts performed interesting catalytic activity in reaction of the cyclohexane oxidation with air, indicating that increasing Co2+ content lowers the initiation temperature and raises the decomposition of cyclohexylhydroperoxide.