Single-molecule magnet materials owe their function to the presence of significant magnetic anisotropy, which arises from the interplay between the ligand field and spin-orbit coupling, and this is responsible for setting up an energy barrier for magnetic relaxation. Therefore, chemical control of magnetic anisotropy is a central challenge in the quest to synthesize new molecular nanomagnets with improved properties. There have been several reports of design principles targeting such control; however, these principles rely on idealized geometries, which are rarely obtained in crystal structures. Here, we present the results of high-pressure single-crystal diffraction on the single-ion magnet, Co(SPh)(4)(PPh4)(2), in the pressure range of 0-9.2 GPa. Upon pressurization a sequence of small geometrical distortions of the central CoS4 moeity are observed, enabling a thorough analysis of the magneto-structural correlations. The magneto-structural correlations are investigated by theoretical analyses of the pressure-dependent experimental molecular structures. We observed a significant increase in the magnitude of the zero-field splitting parameter D, from -54.6 cm(-1) to -89.7 cm(-1), which was clearly explained from the reduction of the energy difference between the essential d(xy) and d(x2-y2) orbitals, and structurally assigned to the change of an angle of compression of the CoS4 moeity.