New　mono-　and　di-anchoring　organic　photosensitizers　(PSs)　with　phenyl　or　triphenylamine　(TPA)　9,9-substituted　fluorene　spacer　and　cyanoacrylic　acid　acceptor(s)　were　synthesized　and　evaluated　for　photocatalytic　hydrogen　generation　from　water.　Their　photophysical　and　electrochemical　properties　were　studied,　focusing　on　their　correlation　with　photocatalytic　performance.　Di-anchoring　PSs　showed　double　the　photocatalytic　efficiency　due　to　their　lower　LUMO　level　and　two　acceptor　groups,　facilitating　efficient　electron　extraction,　reducing　aggregation　on　TiO2,　enhancing　light-harvesting　abilities,　and　improving　charge　transfer.　The　PSs　with　substituted　TPA　adopted　highly　bulky　molecular　structures.　The　introduction　of　TPA　groups　specifically　led　to　the　suppression　of　charge　transport　resistance　and　enhancement　of　interfacial　electron　transfer.　The　TPA-substituted　di-anchoring　PS　TPAF2-based　photocatalytic　system　produced　1380　μmol　of　hydrogen　over　47　h　under　blue　light,　with　a　turnover　number　(TON)　of　22660,　a　turnover　frequency　(TOFi)　of　1067　h−1,　an　initial　hydrogen　production　activity　(activityi)　of　666850　and　an　apparent　quantum　yield　(AQYi%)　of　11.418.　The　bulky　TPA　moieties　rendered　the　PSs　significantly　photostable,　as　affirmed　by　their　high　hydrogen　production　efficiency　over　257　h　of　prolonged　irradiation,　generating　58.9　mL　of　hydrogen.　This　work　presents　a　strategy　for　constructing　efficient　PSs　for　photocatalytic　hydrogen　generation　from　water.　©　2024　Elsevier　Ltd