Abstract: | Biocompatible fluorescent polymeric nanoparticles (FPNs) are promising luminescent probes in cellular bioimaging, while the fabrication of high‐quantum‐yield FPN using nonconjugated heterochain polymers derived from step‐growth polymerization is still in its infancy. Herein, the nonconjugated polyarylene ether nitrile (PEN) is endowed with aggregation‐induced emission (AIE) feature by incorporation of an AIEgen named of 1,2‐di(4‐hydroxyphenyl)‐1,2‐diphenylethene into macromolecular backbone. Furthermore, the AIE‐active PEN is crosslinked into water soluble fluorescent nanospheres showing good biocompatibility and strong emission ≈480 nm with a quantum yield of 21% in the presence of Ca2+, which allows the successful bioimaging of cancer cells. Due to the facile fabrication of FPNs and their effective bioimaging performance, the current work will open the way for the biomedical applications of various high performance polyarylene ethers. |