Sequential reaction of two different hemilabile ligands (Ph2PCH2-CH2X)(2)Ar (X = S, Ar = C6H4 or C-6(CH3)(4); X = NCH3, Ar = C6H4; X = O, Ar = 9,10-C14H8) with a Rh(I) metal center resulted in the formation of heteroligated metallomacrocycles in high yield. The specific reaction conditions for each pair of hemilabile ligands are discussed. The solid-state structure of [{1,4-(Ph2PCH2CH2S)(2)C6H4}-{1,4-(Ph2PCH2CH2S)(2)C-6(CH3)(4)}Rh-2](BF4)( 2), as determined by X-ray crystallography, is presented.