Photochromic symmetrical diarylethenes 1o– 5o bearing different electron-donating or electron-withdrawing substitutents have been synthesized, and the structures of 1o, 2o, 4o, and 5o were determined by single-crystal X-ray diffraction analysis. Substitutent effects on their optoelectronic properties, including photochromism, fluorescence, and electrochemical properties were investigated in detail. The electron-withdrawing substituents can shift significantly the absorption maxima of the diarylethenes to a longer wavelength and increase their cyclization quantum yield, while the molar absorption coefficients increased with an increasing electron-donating ability. Diarylethenes 1, 2, and 4 show good photochromism both in solution and in the single crystalline phase; however, diarylethenes 5 show no photochromism in the crystalline phase because the distance between the reactive carbons become larger than 4.2 Å. Diarylethenes 1– 3 exhibited good fluorescent switching upon alternating irradiation with UV and visible light, and their fluorescent conversions in the photostationary state were all larger than 80% in hexane. In addition, cyclic voltammetry tests showed that different electron-donating and electron-withdrawing substituents had a remarkable effect on the electrochemical behaviors of these diarylethenes.