A novel phosphoranido complex of rhodium(III) porphyrin was prepared by the reaction of a lithium phosphoranide, generated from a P-H phosphorane bearing two 8-oxy-1-naphthyl groups, with (TPP)RhCl (TPP = dianion of 5,10,15,20-tetraphenylporphyrin). The crystal structure of the complex was determined by X-ray structural analysis.