The present investigation describes the synthesis of the ligand 2-((2-hydroxyethylimino)methyl)-6-methoxyphenol (H2L) and its complex of Mn(III) cation. The structure of the compound was elucidated by spectroscopic study and X-ray diffraction for the complex formulated as [{Mn(μ–HL)2}(C2N3)]n. The complex crystallizes in the monoclinic space group P21/n with the following unit cell parameters: a = 5.8172 (3) Å, b = 11.8695 (7) Å, c = 17.2616 (11) Å, b = 96.565 (6)°, V = 1178.57 (12) Å3, Z = 2, R1 = 0.0603 and wR2 = 0.1516. For this compound, the structure reveals that two monodeprotonated ligand interact with one Mn(III) in bidentate fashion while the third coordination site of the ligand interact with another Mn(III) of a neighboring unit. Thus, a polymeric coordination complex is obtained. The Mn(III) is hexacoordinated and the coordination environment can be described as slightly distorted octahedral geometry. Numerous hydrogen bonds link the molecules into three-dimensional network.