Nineteen diiodophosphoranes, R,PI, (R, = Ph,, substituted triaryl, mixed arylalkyl, or trialkyl), the vast majority of which have previously not been reported, are described. Their "PP(H} NMR data indicate an ionic [R,PI]I structure in CDCI, solution, in keeping with results of other solution studies of a limited number of dihalogenophosphoranes, but solid-state ,lP-{H} magic angle spinning NM R data for R,PI, (R, = Ph,, PhMe, or Me,) indicate a molecular four-co-ordinate R,P-1-1 structure, strongly suggesting that this is the common structure for diiodophosphoranes, and not the five-co-ordinate trigonalbipyramidal structure of conventional wisdom.