Elevating　the　long-wavelength　activation　of　photocatalysts　represents　a　formidable　approach　to　optimizing　sunlight　utilization.　Polythiophene　(PTh),　although　renowned　for　its　robust　light　absorption　and　excellent　conductivity,　is　largely　overlooked　for　its　potential　as　a　photocatalyst　due　to　the　swift　recombination　of　photogenerated　charge　carriers.　Herein,　we　unveil　that　the　strategic　introduction　of　an　aromatic　ring　containing　varying　nitrogen　content　into　PTh　instigates　polarized　charge　distribution　and　facilitates　the　narrowing　of　the　band　gap,　thereby　achieving　efficient　photocatalytic　activities　for　both　hydrogen　and　hydrogen　peroxide　generation.　Notably,　the　best　sample,　PTh-N2,　even　demonstrates　photocatalytic　activity　in　the　red　light　region　(600–700　nm).　This　study　offers　a　promising　avenue　for　the　development　of　polymer　photocatalysts　with　efficient　photocatalytic　performance　for　red　light-induced　photocatalysis.　©　2025　Wiley-VCH　GmbH.