The reaction of the trinuclear oxo-centered mixed-valence complex [Mn3O(O2CPh)6(Py)2(H2O)] with 2,2′-bipyridyl (Bipy) and another potential tripodal ligand affords the title compound [Mn3(PhCO2)6(Bipy)2] · H2O in good yield. The X-ray crystallographic diffraction study reveals that three mangenese ions are arranged in a linear mode with Mncenter-Mnterminal and Mnterminal-Mnterminal diatances of 3.588 and 7.176 A, respectively. Molar magnetic susceptibility of the compound gradually decreases from 12.23 (300 K) to 4.45 cm3 K mol−1 (2 K). Taking into account the structure of this compound, the data in the 2.0–300 K range were fit to the appropriate theoretical expression to give J = −2.73 cm−1, ρ = 2.07%, Na = −0.0004 cm3 mol−1, g = 1.992, and R2 = 0.99996. The magnetization versus external magnetic field measurements at 2 K shows that the ground state is ST = 5/2.