Recrystallization of [Co(3,5-dbbq)2(L)2] (3,5-dbbq = 3,5-di-tert-butyl-1,2-benzoquinone; L = bis(3-pyridyl)phenylvinylsilane) from diethyl ether at −20 °C produces trans-[Co(3,5-dbbq)2(L)2] while the recrystallization from toluene at −20 °C gives trans-[Co(3,5-dbbq)2(L)2]·2PhMe. The complex exists as trans-[CoIII(3,5-dbsq)(3,5-dbcat)(L)2] (3,5-dbsq = 3,5-di-tert-butyl-1,2-semiquinonato; 3,5-dbcat = 3,5-di-tert-butylcatecholato) in the solid state at 173 K. Differences in charge distribution between trans-[Co(3,5-dbbq)2(L)2] and trans-[Co(3,5-dbbq)2(L)2]·2PhMe have been observed based on the effective magnetic moments and IR spectra of the complexes along with their X-ray crystal structures.