The article reviews recent progress in nonconventional luminescent macromolecules (NCLMs) and their applications. NCLMs, which lack traditional π-conjugated structures, exhibit excellent biocompatibility, ease of preparation, and unique luminescence behavior. Despite their advantages, the detailed luminescent mechanism of NCLMs remains controversial, and extensive studies are needed to further explore it. The article highlights recent advancements in molecular design, mechanism exploration, applications, and challenges in NCLMs. It discusses the classification and summary of these advances, aiming to provide guidance and inspiration for the development of NCLMs. Key points include: 1. **Molecular Design**: NCLMs are designed to exhibit enhanced emission due to limited intramolecular migration, similar to Aggregation-Induced Emission (AIE). Examples include polyethers, polyesters, proteins, and polysiloxanes. 2. **Mechanism Exploration**: The luminescence of NCLMs is believed to be due to through-space conjugation (TSC) of overlapping electron orbitals in solid/aggregate states. However, the exact mechanism is still under debate. 3. **Applications**: NCLMs have found applications in sensing, optoelectronic displays, anticounterfeiting, and biomedical fields. They are particularly useful in multidimensional information encryption, anti-counterfeiting, and biological analysis. 4. **Challenges and Prospects**: Despite their potential, NCLMs face challenges such as low quantum yields and difficulty in regulating their luminescence properties. Further research is needed to optimize their structure and performance. The article emphasizes the need for more comprehensive experimental and theoretical work to deepen the understanding of NCLMs and to develop them for practical applications.The article reviews recent progress in nonconventional luminescent macromolecules (NCLMs) and their applications. NCLMs, which lack traditional π-conjugated structures, exhibit excellent biocompatibility, ease of preparation, and unique luminescence behavior. Despite their advantages, the detailed luminescent mechanism of NCLMs remains controversial, and extensive studies are needed to further explore it. The article highlights recent advancements in molecular design, mechanism exploration, applications, and challenges in NCLMs. It discusses the classification and summary of these advances, aiming to provide guidance and inspiration for the development of NCLMs. Key points include: 1. **Molecular Design**: NCLMs are designed to exhibit enhanced emission due to limited intramolecular migration, similar to Aggregation-Induced Emission (AIE). Examples include polyethers, polyesters, proteins, and polysiloxanes. 2. **Mechanism Exploration**: The luminescence of NCLMs is believed to be due to through-space conjugation (TSC) of overlapping electron orbitals in solid/aggregate states. However, the exact mechanism is still under debate. 3. **Applications**: NCLMs have found applications in sensing, optoelectronic displays, anticounterfeiting, and biomedical fields. They are particularly useful in multidimensional information encryption, anti-counterfeiting, and biological analysis. 4. **Challenges and Prospects**: Despite their potential, NCLMs face challenges such as low quantum yields and difficulty in regulating their luminescence properties. Further research is needed to optimize their structure and performance. The article emphasizes the need for more comprehensive experimental and theoretical work to deepen the understanding of NCLMs and to develop them for practical applications.