Conjugated　polymers　(CPs)　have　been　demonstrated　to　be　excellent　solar　energy　conversion　materials,　however,　it　is　considered　that　pure　CPs　are　not　able　to　photocatalyze　water　splitting　because　of　the　fast　recombination　of　photogenerated　charge　carriers.　Here,　we　found　polythiophene　(PTh)　nanofibrous　structure　can　have　a　decent　photocatalytic　activity　(2.19　mmol　h(-1)　g(-1))　and　stability　in　ascorbic　acid　aqueous　solution　under　visible　light　irradiation.　Furthermore,　PTh　synthesized　at　high　temperature　will　introduce　structure　defects,　such　as,　alpha-beta＇　coupling　and　end　groups,　which　are　beneficial　to　the　charge　separation.　In　addition,　PTh　synthesized　at　low　temperature　has　long　polymer　chain　and　ordered　arrangement　of　chain,　which　enhanced　the　light　adsorption.　Considering　both　light　adsorption　and　charge　separation,　PTh　compound　nanostructure　was　rationally　designed,　PTh　synthesized　at　low　temperature　as　core　to　obtain　good　light　adsorption　and　PTh　prepared　at　high　temperature　as　sheath　to　form　more　structure　defects　to　promote　charge　separation.　This　PTh　compound　nanostructure　exhibit　higher　photocatalytic　H-2　production　performance　(2.8　mmol　h(-1)　g(-1)).　Our　finding　may　open　a　door　for　conjugated　polymer　for　photocatalyst.　(C)　2017　Elsevier　B.V.　All　rights　reserved.