[Mn(SCN)2(L)4/2] where L = py, γ-pic, pyCH2OH, py–NH–py (dpa) complexes have been prepared and studied by IR and UV-Vis spectroscopy, and X-ray crystallography. Electronic structures of the complexes were calculated using DFT method, and the descriptions of frontier molecular orbitals and the relocation of the electron density of the compounds were determined. The differences in acceptor properties of the used pyridine derivatives ligands were shown in the values of ligand field parameters determined from electronic spectra of the complexes. The magnetic properties revealed paramagnetic behavior with a weak ferromagnetic interaction and the van Vleck contribution for [Mn(SCN)2(py)4] (1), ideal paramagnetism for [Mn(SCN)2(γ-pic)4] (2) and a weak antiferromagnetic interaction and diamagnetic contribution for [Mn(SCN)2(pyCH2OH)2] (3).