Attachment of difluoroborylcobaloxime catalysts to a polymer-brush-modified GaP semiconductor allows improved hydrogen production levels and photoelectrochemical performance under aqueous acidic conditions (pH = 4.5) as compared to the performance of electrodes without catalyst treatment. The catalytic assembly used in this work incorporates a boron difluoride (BF2) capping group on the glyoximate ligand of the catalyst, a synthetic modification previously used to enhance the stability of nonsurface-attached complexes toward acid hydrolysis and to shift the cobalt reduction potentials of the complex to less negative, and thus technologically more relevant, values. The pH-dependent photoresponses of the cobaloxime- and difluoroborylcobaloxime- modified semiconductors are shown to be consistent with those from analogous studies using non-surface-attached cobaloxime catalysts as well as catalysts supported on conductive electrodes. Thus, this work illustrates the potential to control and optimize the properties of visible-light-absorbing semiconductors using polymeric overcoating techniques coupled with the principles of synthetic molecular design.Keywords: artificial photosynthesis; interfaces; photoelectrochemistry; solar fuels;