Two bis(mu-phenoxo)dicopper(II) complexes, [(L-CH3)(2)Cu-2] (1) and [(Lt-Bu)(2)Cu-2] (2), where L-CH3 and Lt-Bu represent the dianions of (methylamino)-N,N-bis(2-methylene-4,6-dimethylphenol) and of (methylamino)-N,N-bis(2-methylene-4,6-di-tert-butylphenol), respectively, are reported to demonstrate the effect of remote substituents on the nature of exchange coupling interactions between the copper(II) centers. In contrast to 1, which is as usual antiferromagnetically coupled, complex 2 is a rare example of a ferromagnetically coupled diphenoxodicopper(II) complex.