Six　donor-donor-π-acceptor　(D-D-π-A)　triphenylamine-based　starburst　organic　dyes　with　different　electron-donating　moieties　and　thiophene-based　π-linkers　were　synthesized　and　characterized.　Their　photophysical　and　electrochemical　properties,　together　with　their　photocatalytic　hydrogen　evolution　performance　as　photosensitizers　(PSs),　were　investigated.　Distinctive　and　prolonged　hydrogen　evolution　performances　of　these　PSs　under　visible-light　irradiation　from　water　in　their　platinized　TiO2　composites　were　demonstrated:　a　turnover　number　(TON)　of　up　to　24　»900　(252　h)　with　1560　μmol　(37.6　mL)　hydrogen　produced,　an　initial　turnover　frequency　(TOFi)　of　1130　h-1,　initial　activity　(Activityi)　of　705　mmol　g-1　h-1,　and　initial　apparent　quantum　yield　(AQYi)　of　12.1%.　To　the　best　of　our　knowledge,　according　to　the　TOF　and　TON　values,　the　designed　PS　system　is　one　of　the　most　efficient　and　robust　photocatalytic　H2　generation　systems　adopting　a　TiO2-anchoring　molecular　PS　in　the　literature.　The　results　showed　that　the　starburst　triarylamine　donor　moiety　with　phenothiazine　functionality　and　the　alkyl　chain　on　the　thiophene　π-linker　could　boost　the　performance　and　longevity　of　the　photocatalytic　system,　providing　a　powerful　strategy　for　the　development　of　starburst-based　highly　efficient　and　robust　D-D-π-A　organic　photosensitizers　in　the　future.　©　2022　American　Chemical　Society.