The coupling of bis(xylylisocyanide) complex of Pd(II) with 1,2,4-thiadiazole-5-amines leads to the formation of an equilibrium mixture of the binuclear complexes. In each of the studied cases, one of the formed complexes is the kinetic product, and the other one is the thermodynamic product. The complexes which are thermodynamic products have been isolated in the pure form and characterized by means of high-resolution mass spectrometry, IR and NMR spectroscopy, and X-ray diffraction analysis. NMR study of the regioisomerization in a solution has revealed that the relative stability of the thermodynamic products in comparison with the kinetic ones is higher than for the corresponding regioisomers containing 1,3-thiazole or 1,3,4- thiadiazole fragment.