Iron (II) and iron (III) complexes, [FeII(DEDTC)2(dppe)] · CH2Cl2 (1), [FeII(ETXANT)2(dppe)] (2) (DEDTC = diethyldithiocarbamate, ETXANT = ethyl xanthate, dppe = 1,2-bis (diphenylphosphino) ethane), and [FeIII(DEDTC)2(dppe)] [FeIIICl4] (3) have been synthesized and characterized. Since 3 contains two magnetic centers, an anion metathesis reaction has been conducted to replace the tetrahedral FeCl4− by a non-magnetic BPh4− ion producing [FeIII(DEDTC)2(dppe)]BPh4 (4) for the sake of unequivocal understanding of the magnetic behavior of the cation of 3. With the similar end in view, the well-known FeCl4− ion, the counter anion of 3, is trapped as PPh4[FeIIICl4] (5) and its magnetic property from 298 to 2 K has been studied. Besides the spectroscopic (IR, UV–Vis, NMR, EPR, Mass and XPS) characterization of the appropriate compounds, especially 2, others viz. 1, 3 and 4 have been structurally characterized by X-ray crystallography. While FeII complexes, 1 and 2, are diamagnetic, the FeIII systems, namely the cations of 3, and 4 behave as low-spin (S = 1/2) paramagnetic species from 298 to 50 K. Below 50 K 3 shows gradual increase of χMT up to 2 K suggesting ferromagnetic behavior while 4 exhibits gradual decrease of magnetic moment from 60 to 2 K, indicating the occurrence of weak antiferromagnetic interaction. These conclusions are supported by the Mössbauer studies of 3 and 4. The Mössbauer pattern of 1 exhibits a doublet site for diamagnetic (2–400 K) FeII. The compounds 1, 2 and 4 encompass interesting cyclic voltammetric responses involving FeII, FeIII and FeIV. ; The authors namely T.K.J., D.P.K., S.D. and R.B. thank Department of Science and Technology (DST), Govt. of India for financial assistance in the form of a Project (Project No. SR/S1/IC-12/2002). T.K.J. thanks DST and D.P.K. thank CSIR, Govt. of India, for fellowship. The magnetic and Mössbauer studies have been supported by the Centre Franco-Indien pour 1a promotion de 1a Recherche Avancee/Indo-French Centre for the Promotion of Advanced Research under Project No. 3108-3. ; Peer Reviewed