The title compound, [Rh(C10H15)(C4H4N2)(C2H3N)2](PF6)2 or [Cp*Rh(NCMe)2(N2C4H4)](PF6)2, where Cp* is pentamethylcyclopentadienyl, was obtained from the treatment of an acetonitrile solution of [Cp*Rh(NCMe)3](PF6)2 with an excess of pyrimidine. The RhIII center is coordinated by one Cp* ring, two acetonitrile ligands and one pyrimidine ligand in a pseudo-octahedral geometry. Both PF6 anions are disordered (site occupancies ca 0.4:0.6, and 0.3:0.4:0.3).