Nonconventional luminescent macromolecules (NCLMs) offer advantages such as biocompatibility, ease of preparation, and unique luminescence behavior, making them promising for optoelectronics, biology, and medicine. Unlike traditional luminescent macromolecules, NCLMs lack conjugated structures and rely on through-space conjugation for intrinsic luminescence. However, the exact mechanism of their luminescence remains debated, requiring further research. Recent advances in NCLMs focus on molecular design, mechanism exploration, and applications, aiming to enhance their photophysical properties and practical potential. NCLMs exhibit enhanced emission due to limited intramolecular migration, similar to Aggregation-Induced Emission (AIE) materials. Examples include polyethers, polyesters, proteins, and polysiloxanes. Their luminescence arises from electron cloud overlap and through-space conjugation, which inhibits quenching and nonradiative relaxation. NCLMs have low raw material costs, simple synthesis, and wide applications in sensing, optoelectronics, and biomedical fields. The emission mechanism of NCLMs is still unclear, with challenges in regulating their photophysical properties across the visible range. Strategies to enhance luminescence include introducing heteroatoms, altering steric confinement, and increasing electron-rich units. Recent studies show that rigid chain structures optimize segmental motion, leading to stable clusters and enhanced luminescence. Blue NCLMs, such as polypeptides and carbonyl polymers, emit due to (n-π*) transitions. Long-wavelength emissions are achieved through through-space charge transfer (TSCT) and through-space interactions (TSI), which enhance electronic communication and red-shifted emission. Heating and microenvironment changes also regulate NCLM luminescence, with pH and temperature affecting emission color. NCLMs with long lifetime luminescence, such as delayed fluorescence (DF) and room-temperature phosphorescence (RTP), show potential for functional materials. RTP is achieved through spin-orbit coupling and intersystem crossing, with hydrogen bonding and crystallization playing key roles. NCLMs with circularly polarized phosphorescence (CPP) offer applications in chiral sensing and encryption. Despite their potential, NCLMs face challenges in achieving high quantum yields (QY) and controlling aggregate structures. Research continues to optimize chain structures, incorporate electron-rich heteroatoms, and develop new strategies to enhance luminescence efficiency. These advancements aim to expand the applications of NCLMs in practical fields.Nonconventional luminescent macromolecules (NCLMs) offer advantages such as biocompatibility, ease of preparation, and unique luminescence behavior, making them promising for optoelectronics, biology, and medicine. Unlike traditional luminescent macromolecules, NCLMs lack conjugated structures and rely on through-space conjugation for intrinsic luminescence. However, the exact mechanism of their luminescence remains debated, requiring further research. Recent advances in NCLMs focus on molecular design, mechanism exploration, and applications, aiming to enhance their photophysical properties and practical potential. NCLMs exhibit enhanced emission due to limited intramolecular migration, similar to Aggregation-Induced Emission (AIE) materials. Examples include polyethers, polyesters, proteins, and polysiloxanes. Their luminescence arises from electron cloud overlap and through-space conjugation, which inhibits quenching and nonradiative relaxation. NCLMs have low raw material costs, simple synthesis, and wide applications in sensing, optoelectronics, and biomedical fields. The emission mechanism of NCLMs is still unclear, with challenges in regulating their photophysical properties across the visible range. Strategies to enhance luminescence include introducing heteroatoms, altering steric confinement, and increasing electron-rich units. Recent studies show that rigid chain structures optimize segmental motion, leading to stable clusters and enhanced luminescence. Blue NCLMs, such as polypeptides and carbonyl polymers, emit due to (n-π*) transitions. Long-wavelength emissions are achieved through through-space charge transfer (TSCT) and through-space interactions (TSI), which enhance electronic communication and red-shifted emission. Heating and microenvironment changes also regulate NCLM luminescence, with pH and temperature affecting emission color. NCLMs with long lifetime luminescence, such as delayed fluorescence (DF) and room-temperature phosphorescence (RTP), show potential for functional materials. RTP is achieved through spin-orbit coupling and intersystem crossing, with hydrogen bonding and crystallization playing key roles. NCLMs with circularly polarized phosphorescence (CPP) offer applications in chiral sensing and encryption. Despite their potential, NCLMs face challenges in achieving high quantum yields (QY) and controlling aggregate structures. Research continues to optimize chain structures, incorporate electron-rich heteroatoms, and develop new strategies to enhance luminescence efficiency. These advancements aim to expand the applications of NCLMs in practical fields.