Abstract Several configurationally constrained cis- and trans-1,2-diaryl-1,2-dimethyl-1,2-disilacyclohexanes (3a–e) have been synthesized in order to measure their photophysical properties, such as UV absorption, magnetic circular dichroism (MCD), and photoluminescence. As has been well established, the UV absorption maximum (1La band) occurs at 230–270 nm, due to the effective σ–π conjugation between the aryl groups and the disilane moiety. The absorption maximum wavelength of the trans isomer is slightly longer than that of the cis isomer for all the diaryldisilanes employed in the present study. Although the MCD spectra of the cis- and trans-1,2-diphenyl-1,2-dimethyl-1,2-disilacyclohexanes (3a) show only a slight configuration dependence, this method is helpful to detect a weak 1Lb band. The disilanes 3a and 5a show a charge-transfer (CT) emission band. The quantum yields are dependent on the disilane configuration and the solvent polarity; the order of the quantum yield is cis-3a < 5a < trans-3a in 3-methylpentane, while the order is 5a < cis-3a < trans-3a in acetonitrile. These results demonstrate that the conformation constraint is effective for controlling the photophysical properties of the diaryldisilanes.