Four linear trinuclear manganese complexes containing ligands with an N 2 O 2 donor set have been prepared and characterized structurally and magnetically. The complexes have the general formula [Mn 3 (L n ) 2 (OAc) 2 (OCH 3 ) 2 ] (n=1, 2, 3, 4. H 2 L 1 =N,N′-dimethyl-N,N′-(2-hydroxy-4,5-dimethylbenzyl)ethylenediamine, H 2 L 2 =N,N-bis(3,4-dimethyl-2-hydroxybenzyl)-N-(2-pyridylmethyl)amine, H 2 L 3 =N,N-bis(3,4-dimethyl-2-hydroxybenzyl)-N,N′-dimethylethylenediamine, H 2 L 4 =N,N-bis(3,4-dimethyl-2-hydroxybenzyl)-2-aminoethanol). X-ray single-crystal structure analyzes of the complexes show that the linear Mn III –Mn II –Mn III cores are triply bridged by phenolate, acetate (syn–syn), and MeO − groups with the Mn III and Mn II distances in the range 3.123(3)–3.167(4)Å. Magnetic studies show that the spin exchange coupling constants (J) between Mn III and Mn II ions range from −1.58(1) to 1.15(3)cm −1 (Hˆ=-2J(Sˆ1·Sˆ2+Sˆ1·Sˆ3)). The antiferromagnetic and ferromagnetic interactions were analyzed based on the structural features, and the Mn III –O–Mn II bond angles have been found to be the dominant factor affecting the intermetallic magnetic coupling.