Two new classes of chiral side-chain polymers comprising a variously spaced biphenyl unit as both a mesogenic core and a fluorescent chromophore were investigated. The chiral group was either a 2,3- or a 2,2-disubstituted oxirane ring. The structures of the smectic phases (A, B, or E) were investigated by X-ray diffraction. Excimer fluorescence emission was detected at room temperature in the smectic phase.