Photochromic unsymmetrical diarylethenes 1a–5a that bear different electron-donating or electron-withdrawing substitutes have been synthesized, and the structures of 2a–5a determined by single-crystal X-ray diffraction analysis. Substituent effects on their optoelectronic properties, including photochromism, fluorescence, and electrochemical properties are investigated in detail. The strong electron-donating substituents have effective contributions to the absorption maxima of the closed-ring isomers and the molar coefficients, whereas the electron-withdrawing substituents can shift significantly the absorption maxima of the diarylethenes to a longer wavelength and increase their cyclization quantum yield. Diarylethenes 2, 3, and 4 show good photochromism both in solution and in the single crystalline phase. However, diarylethenes 5 shows no photochromism in the crystalline phase. Diarylethenes 1, 2, and 3 exhibit good fluorescent switching upon alternating irradiation with UV and visible light, and their fluorescent conversions in the photostationary state are all larger than 80% in hexane. In addition, cyclic voltammogram tests show that different electron-donating and electron-withdrawing substituents have a remarkable effect on the electrochemical behaviours of these diarylethenes.