Dye-sensitized photocatalytic H2 generation has been investigated using a metal-free phenothiazine-based donor − acceptor sensitizer (PTZ-GLU) in combination with coadsorbents. The coadsorption of the PTZ-GLU dye, functionalized with a glucose end-group, in combination with a glucose-based coadsorbent, afforded improved photocatalytic activity compared to the absence of coadsorbents, to the use of a conventional (chenodeoxycholic acid) coadsorbent, or by replacing the dye glucose functionality with an alkylchain. The results suggest the strategic role of directional intermolecular dye − coadsorbent interactions on the semiconductor surface, as confirmed by first principles computational modeling, which likely suppressed detrimental recombination processes.