The reduction of CpTi(NPt-Bu-3)Cl-2 with Mg powder in benzene proceeds slowly to give [CpTi(NPt-Bu-3(mu-Cl)](2))12 tli. An X-ray crystallographic study confirmed 1 is a centrosymmetric chloro-bridged dimer in the solid state. A single-crystal EPR study of 1 permitted the determination of the best-fitted values for the diagonal spin Hamiltonian parameters. This appears to be the first EPR single-crystal study of a Ti(III)-Ti(III) dimer. The implications of these data are considered and discussed in light of extended Huckel molecular orbital calculations.