The new derivatives of 3,4-pyridinedicarboximide were synthesised. Experimental measurements were carried out using 1 H NMR spectra, IR spectra, elemental analyses and differential scanning calorimetry. The purpose of this study was to study the thermal stability of these four new compounds and to establish a solid-state polymorphism. Measurements were carried out for samples obtained from ethanol and n-hexane and after a long-time storage.