New hybrid compounds LnCoCl(deg)2 (deg = diethyleneglycolate; Ln = Nd, Sm, Eu, Gd and Ho) have been synthesized by mixing cobalt and rare earth cations in a boiling diethyleneglycol (degH2) medium. Their crystallographic structures have been ab initio solved from synchrotron powder diffraction data. They consist of edge sharing tetrameric sub-units [(Ln2Co2)(deg)4(Cl)2] forming 1D infinite chains along the c parameter of a monoclinic unit cell (SG = C2/c). The five- and seven-coordination of Co(2+) and Ln(3+) cations inferred from the crystallographic results is confirmed by UV-visible absorption and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. In the LnCoCl(deg)2 (Ln = Nd, Sm, Eu, Gd, Ho) series, weak antiferromagnetic superexchange interactions have been evidenced, between high spin Co(2+) and Ln(3+) orbitally degenerate cations. These materials are considered as potential precursors for the simultaneous reduction of Co-Ln-glycolate species into bimetallic nanoparticles by the polyol process.