A few chiral azo compounds, which undergo reversible photochemical switching, are presented. Of these, the most interesting contain the binaphthyl moiety and belong to the C2 (derivatives 1 and 2) or C1 symmetry group (derivatives 3 and 4). These binaphthyl compounds display intense CD and high beta values. Photochemical switching has profound effects on both the CD and beta values of these compounds; in the case of compound 3, the sign of beta changes upon isomerisation. Compound 2 has, to our knowledge, the highest beta of the switches reported in the literature and also seems the most interesting owing to its fast response to photochemical stimuli. Nematic phases can be transformed into cholesteric phases with reflection bands in the visible region by doping with reasonable amounts of 1 and 2. The reflection colours can be changed reversibly by photoisomerisation of the switches. Thermal reversion of the colourless UV photostationary state to the green isomeric EE state or to intermediate coloured states is temperature dependent. This can allow the thermal history of a sample to be traced.