Controlled organization of high-spin complexes and single-molecule magnets is a great challenge in molecular magnetism in order to study the effect of the intercomplex magnetic interactions on the intrinsic properties of a given magnetic object. In this work, a new S(T) = 7 trinuclear mixed-valence Mn complex, [Mn(III)Mn(II)2(LA)2(Br)4(CH3OH)6] ·Br·(CH3OH)(1.5)·(H2O)(0.5) (1), is reported using a pyridinium-functionalized 1,3-propanediol ligand (H2L(A)Br = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)pyridinium bromide). Using azido anions as bridging ligands and different pyridinium-functionalized 1,3-propanediol ligands (H2L(B)Br = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-4-picolinium bromide; H2L(C)Br = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-3,5-lutidinium bromide), the linear [Mn(III)Mn(II)2L2X4](+) building block has been assembled into one-dimensional coordination networks: [Mn(III)Mn(II)2(LA)2(Br)4(CH3OH)4(N3)]·((C2H5)2O)1.25 (2∞), [Mn(III)Mn(II)2(L(B))2(Br)4(C2H5OH)(CH3OH)(H2O)2(N3)]·(H2O)0.25 (3∞), and [Mn(III)Mn(II)2(L(C))2(Cl)(3.8)(Br)(0.2)(C2H5OH)3(CH3OH)(N3)] (4∞). The syntheses, characterization, crystal structures, and magnetic properties of these new [Mn3]-based materials are reported.