Triphenylpnictogens EPh3 (E = N, P, As, Sb, Bi) are able to displace the perfluorinated Cp* ligand in [Rh(COD)(C5(CF3)5)] (COD = 1,5‐cyclooctadiene) in up to quantitative yield. The resulting ionic products contain [C5(CF3)5]− as uncoordinated counter anion. The cations feature [Rh(COD)]+ fragments, coordinated by one (N, Bi), two (P, As) or three (Sb) triphenylpnictogen moieties. Whereas coordination via the pnictogen is observed for P, As and Sb, π‐coordination of the aryl rings is observed for N and Bi.