A novel sol-gel method has been adopted to synthesize the cubic structure of CoFe2O4 microspheres (CFOM) with JCPDs card no. 22-1086 and polyacrylamide decorated CoFe2O4 microspheres (p-CFOM). The crystal structure, functional group, surface morphology, light absorption capacity, magnetic, photoluminescence and electrochemical properties and photocatalytic activity of CFOM and p-CFOM for the photocatalytic degradation of Congo red (CR) dye have been systematically discussed. The polyacrylamide introduced to the CFOM obviously enhance the light absorption capacity, squareness ratio, photoluminescence properties and charge transfer and separation efficiency. Based on the light absorption, electrochemical measurement and photocatalytic experiments, the p-CFOM possess a higher photocatalytic activity in photocatalytic degradation of CR dye than CFOM. The light absorption capacity, charge transfer and separation efficiency, and photocatalytic experiments of p-CFOM indicated that the polyacrylamide is a linear polymer as a potential electron collector play a key role to restrain charge carrier recombination. Compared with previous reports, some new properties of AFe(2)O(4) could be obtained for different A site metal ions.