A series of new polyanhydrides, +OC(O)ArXC(O)(CH2)(n)C(O)+(m), where Ar was (substituted) phenylene, X was O or NH and n was 2, 3 or 4, was synthesized. Polyanhydride fluorescence was observed only for those with the number of methene groups in the repeating unit (n) being 2. Copolymers based on sebacic acids and the above chromophoric units can also emit light. The relative fluorescence intensity of poly[p-(carboxyethylformamido)benzoic-co-sebacic anhydride] (P(CEFB-SA)) and PCEFB, IP(CEFB-SA)/I-PCEFB, increases with a decrease in the fraction of SA. However, the fluorescence intensity of poly[o-acetyl-p-(carboxyethylformamido)benzoic-co-sebacic anhydride] (P(ACEFB-SA)) reaches a maximum when the ACEFB content is 50%.