Photocatalytic overall water splitting holds great promise for solar-to-hydrogen conversion. Maintaining charge separation is a major challenge but is key to unlocking this potential. Here we discovered a metal-organic framework (MOF) that shows suppressed charge recombination. This MOF features electronically insulated Zn2+ nodes and two chemically equivalent, yet crystallographically independent, linkers. These linkers behave as an electron donor-acceptor pair with non-overlapping band edges. Upon photoexcitation, the MOF undergoes a dynamic excited-state structural twist, inducing orbital rearrangements that forbid radiative relaxation and thereby promote a long-lived charge-separated state. As a result, the MOF achieves visible-light photocatalytic overall water splitting, in the presence of co-catalysts, with an apparent quantum efficiency of 3.09 ± 0.32% at 365 nm and shows little activity loss in 100 h of consecutive runs. Furthermore, the dynamic excited-state structural twist is also successfully extended to other photocatalysts. This strategy for suppressing charge recombination will be applicable to diverse photochemical processes beyond overall water splitting.