The　component　and　structure　of　thermally　poled　and　corona　charged　PVDF　films　were　investigated　by　the　aid　of　high-resolution　X-ray　photoelectron　spectroscopy　(XPS).　The　results　of　XPS　and　ferroelectric　properties　show　that　the　reaction　and　mechanism　of　thermally　poling　and　corona　charging　for　PVDF　films　was　distinct.　With　the　effect　of　high　electric　field　at　high　temperature　in　thermally　poling,　a　new　carbon　couple　bond　was　created　through　the　action　of　HF　which　was　produced　by　F-　radicals.　However,　the　H+　radicals　engendered　due　to　bombardment　of　particles　during　corona　charging.　And　the　remanent　polarization　of　thermally　poled　PVDF　film　is　about　3.5　μC/cm2,　while　that　of　corona　charged　PVDF　film　is　about　3.0　μC/cm2.　©　Copy　Right.