This study presents a method to enable nonconjugated polyesters to emit full-spectrum fluorescence from blue to near-infrared (470–780 nm). The research focuses on the synthesis of nonconjugated polyesters through the copolymerization of epoxides and cyclic anhydrides, catalyzed by organic amines. Amines act as initiators attached to the polymer chain ends, forming stable amine-ester complexes that induce red-to-near-infrared (NIR) clusteroluminescence via intra/inter-chain charge transfer. The emission colors can be easily tuned by the types and contents of amines, microstructures of polyesters, and their concentrations. This work provides a low-cost, scalable platform for producing high-efficiency, multicolor luminescent materials. The study highlights the unique properties of nonconjugated polyesters, which can exhibit clusteroluminescence (CL) through through-space interactions (TSIs). These materials offer advantages such as easy processing, biocompatibility, and the ability to be mass-produced from renewable resources. However, the lack of a universal CL theory has limited the regulation of photophysical performances. The research demonstrates that amine-ester complexes can be engineered to achieve full-spectrum emission, with the highest solid-state quantum yield (QY) of 15.8% for P1-5.0TEA. The study also reveals the role of amine-ester complexes in generating strong TSIs, leading to red-to-NIR CL. Theoretical calculations and NMR characterization confirm the formation of amine-ester complexes, with nitrogen atoms on amines playing a crucial role in red-to-NIR CL. The results show that the emission colors can be manipulated by the molar ratios and types of amine catalysts, chain microstructures of polyesters, and concentration. The study further demonstrates that the formation of amine-ester complexes is essential for achieving red-to-NIR CL, with long-range complexes being responsible for NIR CL. The research provides a sustainable platform for achieving high-efficiency, controllable blue-to-NIR CLgens with deeper insight into CL. The findings suggest that the unique microstructures of polymer chains relative to small molecules are crucial in manipulating photophysical properties. The study concludes that nonconjugated polyesters can emit full-spectrum fluorescence from blue to near-infrared, offering a new approach for the development of luminescent materials.This study presents a method to enable nonconjugated polyesters to emit full-spectrum fluorescence from blue to near-infrared (470–780 nm). The research focuses on the synthesis of nonconjugated polyesters through the copolymerization of epoxides and cyclic anhydrides, catalyzed by organic amines. Amines act as initiators attached to the polymer chain ends, forming stable amine-ester complexes that induce red-to-near-infrared (NIR) clusteroluminescence via intra/inter-chain charge transfer. The emission colors can be easily tuned by the types and contents of amines, microstructures of polyesters, and their concentrations. This work provides a low-cost, scalable platform for producing high-efficiency, multicolor luminescent materials. The study highlights the unique properties of nonconjugated polyesters, which can exhibit clusteroluminescence (CL) through through-space interactions (TSIs). These materials offer advantages such as easy processing, biocompatibility, and the ability to be mass-produced from renewable resources. However, the lack of a universal CL theory has limited the regulation of photophysical performances. The research demonstrates that amine-ester complexes can be engineered to achieve full-spectrum emission, with the highest solid-state quantum yield (QY) of 15.8% for P1-5.0TEA. The study also reveals the role of amine-ester complexes in generating strong TSIs, leading to red-to-NIR CL. Theoretical calculations and NMR characterization confirm the formation of amine-ester complexes, with nitrogen atoms on amines playing a crucial role in red-to-NIR CL. The results show that the emission colors can be manipulated by the molar ratios and types of amine catalysts, chain microstructures of polyesters, and concentration. The study further demonstrates that the formation of amine-ester complexes is essential for achieving red-to-NIR CL, with long-range complexes being responsible for NIR CL. The research provides a sustainable platform for achieving high-efficiency, controllable blue-to-NIR CLgens with deeper insight into CL. The findings suggest that the unique microstructures of polymer chains relative to small molecules are crucial in manipulating photophysical properties. The study concludes that nonconjugated polyesters can emit full-spectrum fluorescence from blue to near-infrared, offering a new approach for the development of luminescent materials.