4,4'-Bipyridine phosphotungtic salt has been synthesized and used as a special catalyst for vinyl polymerization. This is a fast and smooth reaction, and high molecular weight polymers with narrow polydispersity are obtained within 60 min. The compound was structurally characterized by elemental analysis, IR spectroscopy and H-1 NMR spectroscopy. The electrochemical property was determined on a CHI 660 electrochemistry workstation. The polymerization initiated by 4,4'-bipyridine phosphotungtic salt showed controlled characteristics, the catalyst can be isolated from polymer product easily and reused for at least 10 times. (c) 2012 Elsevier B.V. All rights reserved.