Using synchrotron powder diffraction data, two new complexes of CdBr2 with 3‐fluoroaniline and 4‐fluoroaniline were fully characterised with regard to their structure. Their crystal structures were solved and refined by means of powder diffraction techniques. The investigated materials belong to the group of hybrid inorganic–organic coordination polymers. The structures of both compounds are created by the same type, infinite chains formed by CdBr4N2 octahedra. Each cadmium cation is surrounded by four Br− anions, and two N atoms from two fluoroaniline molecules.The obtained structural data enable us to investigate the influence of the position of the F atom in the aniline ring on the crystal structure, as well as to interpret its thermal stability. Copyright © 2015 John Wiley & Sons, Ltd.