This paper reports the synthesis, crystal structures, and magnetic properties of a series of mixed-valence polynuclear manganese complexes bridged by a dianionic 1,2,4-triazole-based ligand L2- (H2L = 3-(2-phenol)-5-(pyridin-2-yl)-1,2,4-triazole). Complexes 1 to 3 show a similar binuclear structure, with the central core of [MnIIMn III(L)2] and some other small molecules also coordinated to the two Mn centers. The two [MnIIMnIII(L)2] subunits can be further connected by different dicarboxylic acids to construct non-charged tetranuclear complexes 4 to 7. In these complexes, each deprotonated dianionic ligand L2- acts as a μ2-bridged ligand to coordinate two Mn centers via the 1,2,4-triazole ring. Bond valence sum (BVS) calculations and Mn surrounding bond lengths indicate that the Mn center coordinated to the pyridine N atoms in the +2 oxidation state, while another Mn center coordinated to the phenolic O atoms is in the +3 oxidation state. The MnIII centre shows Jahn-Teller elongation along one of the axes. Magnetic studies show the presence of ferromagnetic MnIII-Mn II coupling in the binuclear (1-3) and tetranuclear (4-7) complexes with the magnetic coupling constant (J) ranging from 0.58 to 1.17 cm -1, based on the Hamiltonian H = -2JS1·S 2 (S1 = 5/2 and S2 = 2). In all cases both z′J′ (intermolecular interactions) and D parameter (Zero Field Splitting of the Mn (III) ion) has been introduced to improve the corresponding fit. The relationship of the coupling interaction between the Mn II/MnIII and their electronic structures is discussed.