The synthesis of newly designed photochromic dithienylethene-containing ethynylthiophene and ethynylthieno[3,2-b]thiophene has been described, and their incorporation as versatile ligands into the platinum(II) phosphine system was demonstrated. All platinum(II) complexes have been successfully characterized by (1)H and (31)P NMR spectroscopies, positive fast atom bombardment (FAB) mass spectrometry, as well as elemental analysis. One of the complexes has been characterized by X-ray crystallography. Their photophysical, photochromic, and electrochemical properties have been studied. Upon photoexcitation, all the photochromic diarylethene-containing alkynes and platinum(II) complexes exhibited reversible photochromism. The thermal bleaching kinetic of complex 6 was studied in toluene at 298 and 313 K. Complexes 1, 3, and 4, which contained the labile chloro- ligand, represent a new class of versatile building blocks for photoswitchable functional materials.