Two manganese(III)‐dicyanamide compounds, [Mn(5‐Brsalen)(dca)]·CH3OH (1) and [Mn(3‐Meosalphen)(dca)(H2O)] (2) (dca = dicyanamide anion, [N(CN)2]–), were synthesized and characterized by elemental analysis, IR spectroscopy, single‐crystal X‐ray structure analysis, and cyclic voltammetry. The structure of complex 1 is an infinite zigzag chain of hexacoordinate MnIII ions, in which the adjacent manganese atoms are connected by dca in μ1,5‐bridging mode. The molecular structure of complex 2 consists of a hexacoordinate MnIII atom, which generates a slightly distorted octahedral arrangement, and a dimer structure is formed by intermolecular hydrogen bonding interactions. The electrochemical properties of the two complexes were measured by cyclic voltammetry.