This study explores the development of nonconjugated luminophores that emit a full spectrum of light from blue to near-infrared (470–780 nm). The researchers synthesized nonconjugated polyesters through the amine-initiated copolymerization of epoxides and cyclic anhydrides, revealing that amines act as initiators forming stable amine-ester complexes. These complexes induce red to near-infrared light through intra/inter-chain charge transfer. The emission colors can be tuned by the content and type of amines, microstructures of polyesters, and their concentration. The work provides a low-cost, scalable platform for producing high-efficiency, multicolor luminescent materials, offering significant advantages over traditional π-conjugated luminophores in terms of processability, biocompatibility, and environmental friendliness.This study explores the development of nonconjugated luminophores that emit a full spectrum of light from blue to near-infrared (470–780 nm). The researchers synthesized nonconjugated polyesters through the amine-initiated copolymerization of epoxides and cyclic anhydrides, revealing that amines act as initiators forming stable amine-ester complexes. These complexes induce red to near-infrared light through intra/inter-chain charge transfer. The emission colors can be tuned by the content and type of amines, microstructures of polyesters, and their concentration. The work provides a low-cost, scalable platform for producing high-efficiency, multicolor luminescent materials, offering significant advantages over traditional π-conjugated luminophores in terms of processability, biocompatibility, and environmental friendliness.