A single-crystal X-ray diffraction study of the phosphorane, Ph2PCl3, crystallized from toluene, establishes that the compound is covalent and 5-coordinate rather than 4-coordinate and ionic. The trigonal bipyramidal structure with axial chlorines correlates well with previously reported solid-state Raman and solution Cl-37 NQR spectroscopic data. The structural determination is used as a basis for interpreting the widely varied P-31 NMR spectroscopic shifts that have been reported for Ph2PCl3.