Photocatalytic formic acid dehydrogenation (FAD) has been regarded as one of the most promising methods of producing H₂ in a sustainable manner. In the photocatalytic FAD reaction, photogenerated holes play an important role in the reaction mechanism and thus in the efficiency of photocatalysts. However, the design of photocatalytic systems capable of generating high hole potential without compromising the reducing ability of the photocatalyst is extremely rare for the FAD reaction. In this respect, we report herein a novel and highly efficient heterojunction photocatalyst composed of 2D graphitic carbon nitride, 2D MnO₂, 1D MnOOH, and 0D PdAg alloy nanoparticles, denoted as GCN/MnO₂/MnOOH-PdAg, that can create high reduction and oxidation potentials via a dual S-scheme heterojunction. The photocatalysts exhibited a superb photocatalytic activity in the FAD with a record turnover frequency (TOF) of 3919 h⁻¹ under visible light irradiation, which was 6-, 5.2- and 24-times greater than those of GCN-PdAg, GCN/MnO₂-PdAg, and MnO₂/MnOOH-PdAg heterojunctions, respectively. The structure and dual S-scheme mechanism of the photocatalyst have been clearly demonstrated by extensive instrumental analysis, radical trapping tests, and scavenger experiments. More importantly, it was discovered that the presented photocatalyst continued to function with comparable activity in dark for a prolonged time using the same photocatalytic mechanism. The activity of the photocatalyst in dark was attributed to the utilization of electrons stored on Mn₂O₃, which was detected as a 4–5 nm thick layer on the surface of MnOOH nanorods. This study, in addition to being the first example of both a “day/night photocatalyst” for FAD with an S-scheme mechanism, also demonstrates for the first time the boosting of FAD via a dual S-scheme heterojunction photocatalyst.