The trinuclear complex Mn(3)(pko)(4)(CH(3)O)(2)(SCN)(2).CH(3)OH, 1, where Hpko is 2,2'-dipyridylketonoxime, is a rare example of a complex simultaneously containing Mn(II) and Mn(IV). X-ray crystallography and XANES spectroscopy clearly distinguish the Mn(II)(2)Mn(IV) valence isomer from the more commonly observed Mn(III)(2)Mn(II) formulation. Fits to variable-temperature magnetic susceptibility data indicate that the Mn(II) and Mn(IV) are ferromagnetically coupled (J = +6.13 cm(-1)) and that 1 has an S = (13)/(2) ground state.