AbstractVarious polyesters having pendant (9‐anthryl)methyl groups were prepared from 2‐(9‐anthryl)methylpropane‐1,3‐diol and the esters or chlorides of dicarboxylic acids. These polyesters are poly[2‐(9‐anthryl)‐methylpropane‐1,3‐diyl‐oxy‐(9‐anthryl)methylmalonyl‐oxy](PA‐1A), poly‐[2‐9‐anthrylmethylpropane‐1,3‐diyl‐oxysuccinyloxy](PA‐2), poly‐[2‐9‐anthrylmethylpropane‐1,3‐diyl‐oxyadipyloxy](PA‐4), poly[2‐(9‐anthryl)methylpropane‐1,3‐diyl‐oxysebacyloxy] (PA‐8), poly[2‐(9‐anthryl)methylpropane‐1,3‐diyl‐oxy‐(1‐naphthyl)methylmalonyloxy](PA‐1N), and poly[2‐(9‐anthryl)methylpropane‐1,3‐diyl‐oxyterephthaloyloxy](PA‐Ph). Although the absorption spectrum of the anthryl group is not influenced by the change in the environment in which the anthryl group is located, the fluorescence spectra show characteristic change reflecting the environment around the chromophore. Dimer, aggregates, or excimer fluorescence of anthryl groups and energy transfer from naphthyl to anthryl groups for PA‐1N were discussed. The rates of photodimerization of anthryl groups determined spectroscopically in dilute solutions for these polyesters and their monomer model compound(1,3‐diacetoxy‐2(9‐anthryl)methylpropane) (MA), were in the following order; PA‐8 > PA‐4 > PA‐1A > PA‐2 > PA‐Ph > MA. The effects of polymer structure on the photoreaction were discussed on the basis of information on molecular interactions obtained by fluorescence spectroscopy. The fraction of intramolecular cyclization was estimated from dependence of the rate of photoreaction on the concentration of the polyesters. When anthryl groups are linked by a long, flexible polymethylene chain (PA‐8), intramolecular process predominates whereas intermolecular dimerization proceeds almost exclusively for a rodlike molecule(PA‐Ph). These results are discussed from the viewpoint of the structure–functionality relationship in polymeric systems.