Specific bioconjugation for native primary amines is highly valuable for both chemistry and biomedical research. Despite all the efforts, scientists lack a proper strategy to achieve high selectivity for primary amines, not to mention the requirement of fast response for real applications. Herein, in this work, we report a chromone-based aggregation-induced emission (AIE) fluorogen called CMVMN as a self-reporting bioconjugation reagent for selective primary amine identification, and its applications for monitoring bioprocesses of amination and protein labeling. CMVMN is AIE-active and is capable of solid-state sensing. Thus, its electrospun films are manufactured for visualization of amine diffusion and leakage process. CMVMN also shows good biocompatibility and potential mitochondria-staining ability, which provides new insight for organelle-staining probe design. Combined with its facile synthesis and good reversibility, CMVMN not only shows wide potential applications in biology, but also offers new possibilities for molecular engineering.