Nonconventional or nonconjugated luminophore without polycyclic aromatics or extended π-conjugation is a rising star in the area of luminescent materials. However, continuously tuning the emission color within a broad visible region via rational molecular design remains quite challenging because the mechanism of nonconventional luminescence is not fully understood. Herein, we present a new class of nonconventional luminophores, poly(maleimide)s (PMs), with full-color emission that can be finely regulated by anionic polymerization even at ambient temperature. Interestingly, the general characteristics of nonconventional luminescence, cluster-triggered emission, e.g., concentration-enhanced emission, are not observed in PMs. Instead, PMs have features similar to aggregation-caused quenching due to boosted intra/inter-molecular charge transfer. Such a biocompatible luminescent material synthesized from a low-cost monomer shows great prospects in large-scale production and applications, including security printing, fingerprint identification, metal ion recognition, etc. It also provides a new platform of rational molecular design to achieve full-color nonconventional luminescence without any aromatics.