A charge density study of crystalline pentafluorobenzoic acid has been carried out using high-resolution X-ray diffraction data collected at 110 K. Two multipole refinement models based on the rigid-pseudoatom formalism were used for topological analysis, and the results were compared to those of theoretical calculations for the isolated molecule. In an analysis of the topological parameters at the bond critical points, the discussion focuses on the C-F bond, the hydrogen bond, and intramolecular and intermolecular weak (FO)-O-... and (FF)-F-... ' interactions. Moreover, the geometrical distribution of the nonbonded valence shell charge concentrations was studied at oxygen and fluorine atoms on the basis of experimental data.