We report the results of the DC magnetization, neutron powder diffraction and neutron depolarization studies on the spin-chain compounds Ca3Co2–xFexO6 (x = 0, 0.1, 0.2 and 0.4). Rietveld refinement of neutron powder diffraction patterns at room temperature confirms the single-phase formation for all the compounds in rhombohedral structure with space group R
c. Rietveld refinement also confirms that Fe was doped at the trigonal prism site, 6a (0, 0, 1/4) of Co. The high temperature magnetic susceptibility obeys the Curie-Weiss law; the value of the paramagnetic Curie temperature (θp) decreases as the concentration of iron increases and it becomes negative for x = 0.4. No extra Bragg peak as well as no observable enhancement in the intensity of the fundamental (nuclear) Bragg peaks has been observed in the neutron diffraction patterns down to 30 K. No depolarization of neutron beam has been observed down to 3 K confirming the absence of ferro- or ferrimagnetic-like correlation.