Polyimines (PI) are vitrimer materials with unique Schiff base dynamic covalent chemistry. Various inorganic micro or nano fillers have been used to enhance the mechanical properties of PI materials. Inspired by natural biomineralization, a novel polyimine vitrimer composite is designed and prepared via a one‐pot synthesis. Briefly, diethylenetriamine and glutaraldehyde are used as the monomers of the PI matrix. Then a silica precursor, (3‐aminopropyl)trimethoxy silane is employed to develop silica nanoparticles within the formed PI matrix. The in situ generated silica nanoparticles with amine groups could act as the enhancing fillers and the crosslinkers in the artificial biomineralized silica reinforced polyimine composites. The optimized hybrid materials possessed enhanced mechanical properties, heat‐driven malleability, and limited recycling ability. Notably, the silica content (11.7%) is crucial to the mechanical performance of the PI matrix. This method may help to pave a new avenue on the simple fabrication of hybrid composites.