The study of luminescence phenomena in non-conjugated systems, namely clusteroluminescence, has gained significant attention for the development of advanced luminescent materials. While conventional strategies to manipulate the luminescent performances are based on complicated chemical reactions. In contrast, nature employs complexation to modulate luminescence, inspiring researchers to adopt an engineering approach for the construction of efficient clusteroluminogens. In this work, we explore the complexation-induced clusteroluminescence of carbonyl-based polymers with nitrogen-containing organic bases, exemplified by polyamide, polyester, polycarbonate, and poly(monothiocarbonate). The results demonstrate an increase in the intrinsic 440 nm emission of carbonyl groups and the emergence of new emission peaks upon complexation. The study proposes a through-space n‧‧‧π complex mechanism, highlighting the potential of complexation as a strategy for modulating the clusteroluminescent properties of non-conjugated systems. Further research is necessary to unravel underlying mechanisms, optimize cluster structures, and explore new materials for complexation, thereby advancing optoelectronics and photonics fields and enabling practical applications of clusteroluminescent materials.