The synthesis and study of the photo- and thermoresponsive behavior of a series of novel trimesogens consisting of a diphenylbutadiene core linked to cholesterol moieties on either side via flexible alkyl chains are reported. These molecules possess the combined glass-forming properties of bischolesterols and the photochromic and luminescent properties of the butadiene moiety. The pitch of the cholesteric phase of these materials could be continuously varied thermally and photochemically, making it possible to tune the color of the film over the entire visible region. The color images thus generated could be stabilized by converting them to N* glasses. These materials were also highly photoluminescent, exhibiting circularly polarized characteristics in the glassy liquid-crystalline state even by linearly polarized excitation.