Rational　design　of　semiconductor　molecule　structure　is　of　significant　importance　for　achieving　the　multifunctional　photocatalysis.　Herein,　three　end/bay-substituted　perylenediimide　(PDI)　molecules,　including　bis(N-carboxymethyl)　perylenediimide　(H2PDI),　1,7-dibromo-substituted　H2PDI　(2Br-H2PDI)　and　1,6,7,12-tetraether-substituted　H2PDI　(4CH3CH2O-H2PDI),　are　synthesized　for　photocatalytic　oxygen　evolution　(POE)　and　oxygen　reduction　reaction　(ORR).　One-dimensional　H2PDI　nanorods,　two-dimensional　2Br-H2PDI　nanosheets,　and　zero-dimensional　4CH3CH2O-H2PDI　nanoparticles　are　obtained.　Under　visible　light,　4CH3CH2O-H2PDI　as　photocatalyst　(5.31　mmol·g−1·h−1)　exhibits　the　1.8-times　and　20-times　POE　rate　of　2Br-H2PDI　(2.93　mmol·g−1·h−1)　and　H2PDI　(0.26　mmol·g−1·h−1)　with　AgNO3　as　sacrificial　agent.　Additionally,　the　POE　rate　can　be　further　improved　to　9.34　mmol·g−1·h−1　with　the　Co2+　doping　of　4CH3CH2O-H2PDI.　With　isopropanol　as　sacrificial　agent,　the　H2O2　evolution　rate　of　657.4　μM·g−1·h−1　can　be　also　achieved　via　photocatalytic　ORR　with　4CH3CH2O-H2PDI　as　catalyst,　which　is　∼3　and　∼4　times　those　of　2Br-H2PDI　(220.8　μM·g−1·h−1)　and　H2PDI　(160.0　μM·g−1·h−1),　respectively.　Especially,　in　the　O2-　or　air-　saturated　aqueous　solution　without　sacrificial　agent,　the　H2O2　rate　of　273.1　or　112.7　μM·g−1·h−1　can　be　also　achieved.　This　work　provides　a　promising　way　to　design　the　PDI-based　multifunctional　photocatalysts.　©　2024　Elsevier　B.V.