In order to explore new metal coordination polymers and to search for new types of ferroelectrics among hybrid coordination polymers, two manganese dicyanamide complexes, poly[tetramethylammonium [di-μ3-dicyanamido-κ6N1:N3:N5-tri-μ2-dicyanamido-κ6N1:N5-dimanganese(II)]], {[(CH3)4N][Mn2(NCNCN)5]}n, (I), andcatena-poly[bis(butyltriphenylphosphonium) [[(dicyanamido-κN1)manganese(II)]-di-μ2-dicyanamido-κ4N1:N5]], {[(C4H9)(C6H5)3P]2[Mn(NCNCN)4]}n, (II), were synthesized in aqueous solution. In (I), one MnIIcation is octahedrally coordinated by six nitrile N atoms from six anionic dicyanamide (dca) ligands, while the second MnIIcation is coordinated by four nitrile N atoms and two amide N atoms from six anionic dca ligands. Neighbouring MnIIcations are linked together by μ-1,5- and μ-1,3,5-bridging dca anions to form a three-dimensional polymeric structure. The anionic framework exhibits a solvent-accessible void of 289.8 Å3, amounting to 28.0% of the total unit-cell volume. Each of the cavities in the network is occupied by only one tetramethylammonium cation. In (II), each MnIIcation is octahedrally coordinated by six nitrile N atoms from six dca ligands. Neighbouring MnIIcations are linked together by double dca bridges to form a one-dimensional polymeric chain, and C—H...N hydrogen-bonding interactions are involved in the formation of the one-dimensional layer structure.