Four chiral 1,1′‐biphenyls with one or two sulfur‐containing bridges in 2,2′‐ or 2,2′‐ and 6,6′‐positions, viz. 1,11‐dimethyl‐5,7‐dihydrodibenzo[c,e]thiepin (1), its S‐oxide (2) and S,S‐dioxide (3), and the doubly bridged 10,12‐dihydro‐4H,6H‐[2]benzothiepino[6,5,4‐def][2]benzothiepin (4) have been studied by chromatography, CD spectroscopy, X‐ray crystallography, and empirical force‐field and CNDO/S calculations. The structures obtained by force‐field calculations showed good agreement with the crystal structures determined for 2 and 3. Compounds 2, 3, and 4, but not 1, could be resolved into enantiomers by chromatography on swollen microcrystalline triacetylcellulose. The barrier for biphenyl inversion in 2 was found to be higher than 167 kJ⋅mol−1 by an attempted thermal racemization. The CD spectra of the enantiomers of 2 – 4 were recorded and resolved into individual bands, and the corresponding rotational strengths were calculated. The transitions showed considerable similarity to those of a 1,1′‐biphenyl with hydrocarbon bridge (cf. 5), albeit with bathochromic shifts, which permitted the assignment of the absolute configurations of the enantiomers of 2 – 4. The assignments were supported by comparison of the experimental CD spectra with spectra calculated by the CNDO/S method. All first‐eluted enantiomers were found to have the (S)‐configuration.