The charge density of the title compound was determined at 90 K, using a spherical crystal of 150 µm diameter. The proper treatment of the Zn atom in the pseudo‐tetrahedral environment is considered in detail. A satisfactory refinement is only obtained when anharmonic Gram–Charlier parameters are included as variables in the refinement. A successful combined anharmonic/multipole refinement indicates a small polarization of the 4s shell in the anisotropic environment. One of the two toluenethiols is approximately π‐stacked with the phenanthroline ligand. A bond path is found connecting the two ligands. In addition the Zn—S bond to this ligand is slightly extended compared with the same bond to the second toluenethiol. A separate photocrystallographic and theoretical study indicates the long wavelength emission of the title compound to be due to a ligand‐to‐ligand charge transfer (LLCT) from a toluenethiol to the phenanthroline ligand. The charge‐density results do not provide a basis for deciding which of the thiole ligands is the source of the transferred electron density. This result is in agreement with the theoretical calculations, which show comparable oscillator strengths for charge transfer from either of the ligands.