A series of binuclear ruthenium vinyl complexes with dithienylethene units, [RuCl(CO)(PMe3)3]2(μ-CHCH-DTE-CHCH) (5a, 5b), [RuCl(CO)(Py)(PPh3)2]2(μ-CHCH-DTE-CHCH) (6a, 6b), [RuTp(CO)(PPh3)]2(μ-CHCH-DTE-CHCH) (7a, 7b), and [RuCl(CO)(PMP)]2(μ-CHCH-DTE-CHCH) (8a, 8b) (DTE = 1,2-bis(2-methylthiophen-3-yl)cyclopentene; 1,2-bis(2-methylthiophen-3-yl)-3,3,4,4,5,5-hexafluorocyclopentene), have been prepared. The respective products have been characterized by elemental analyses, NMR spectrometry, and UV/vis spectrophotometry. The structures of 3a and 5b have been established by X-ray crystallography. It is revealed that the binuclear ruthenium vinyl complexes with dithienylethene units show photochromic behavior, but their absorption spectra, cyclization/cycloreversion quantum yields, and the efficiency of the photochromic process are highly dependent on the central switching units and the ancillary ligands attached to the metal. Electrochemical studies have shown that the open-ring isomers of the metal complexes are triggered, either by light or electricity, to convert to their closed forms. It has clearly been demonstrated that these complexes represent a class of light- and electrotriggered multifunctional switch molecules featuring electrochromism, electrocyclization, and photo/electrotuning of the electronic communication.