Rh(III) porphyrin complexes with bridging hydrazine and substituted hydrazine ligands were characterized in solution by]H NMR spectroscopy and in the solid state by X-ray diffraction. Addition of further ligand to these species afforded 1:1 complexes in which methylhydrazine and N,N-dimethylhydrazine preferentially bound to the Rh center through the substituted nitrogen atom, as evidenced by H-1 NMR chemical shifts. An alkylated Rh(III) porphyrin was isolated as a decomposition product of the reaction of NN-dimethylhydrazine with Rh(III) porphyrin in the presence of light and oxygen. Me2Se2 and Me2S2 formed bridging and nonbridging complexes with Rh(III) porphyrin, analogous to that observed with N,N'-dimethylhydrazine.