Conventional luminescent materials normally contain large π-aromatic building blocks. In recent decades, intrinsic photoluminescence (PL) from unconventional luminophores in absence of any traditional conjugated luminophores nor aromatic motifs has been demonstrated. In general, these unconventional luminophors involve certain subgroups, such as alkene (C=C), cyano (C≡N), carbonyl (C=O), hydroxyl (-OH), acylamino (-NH-CO-). Although the corresponding emission mechanism remains an open question, it is generally accepted that the emission of these unconventional luminophores is attributed to the aggregation of non-conjugated chromophores (clustering-triggered emission, CTE). In particular, among the emerging luminescent materials, non-conjugated luminescent polymers (NCLPs) synthesized from non-luminescent monomers have aroused increasing interest because of their significant fundamental importance and promising technical applications. Taking advantage of non-conjugated polymeric materials, such as ease of synthesis, high processability, good biocompatibility, and environmental degradation, NCLPs have great potential for applications in bioimaging, anti-counterfeiting, and biosensors, etc. Based on the CTE mechanism, to achieve NCLPs from non-luminescent monomers, several factors need to be fulfilled. These include: (1) the presence of electron-rich heteroatoms, such as O, N, S, P, etc. ; (2) intra-and intermolecular interactions, e.g., dipole-dipole interactions, n-π interactions, that can afford through space electronic communications (3) rigid microenvironment that can inhibit the non-radiative relaxation of the chromophore and promote the photoluminescence efficiency of the chromophore. Therefore, as one intends to design and prepare a new NCLP, it is challenging to simultaneously fulfill all these requirements with a single species of monomer. As the first two issues can be realized by selecting proper monomers with certain pendants, the rigidity of non-conjugated polymers is usually limited due to the relatively high flexibility of main chains, especially for vinyl-based polymers with C-C backbones. In fact, the rigidity of polymer is reflected by the glass transition temperature (Tg), which can be enhanced through introducing conformational restriction around single bonds. Usually, the presence of bulky ring-like side groups can give rise to a high Tg due to the steric restriction of chain mobility. Indeed, copolymerization of two or more species of monomers can be a facile and effective approach to fabricate novel NCLPs with tunable photophysical properties from a wide range.