C2H5NH3Hg(CN)2Cl belongs to the family of materials with one‐dimension structural character. X‐ray diffraction investigations, calorimetric and dielectric measurements show the occurence of a structural phase transition at Tc = 250 K from a quadratic high temperature form (P4/mmm, Z = 2) to a triclinic low temperature form (P1, Z = 2) and corresponding to a slight deformation of the unit cell when decreasing the temperature.