Fiber‐Spinning‐Chemistry Method toward In Situ Generation of Highly Stable Halide Perovskite Nanocrystals

All‐inorganic halide perovskite nanocrystals (PNCs) have drawn increasing attention owing to their splendid optical properties. However, such nanomaterials suffer from intrinsic instability, greatly limiting their practical application. Meanwhile, environmental regulation has restricted the emissions of volatile organic compounds (VOCs), initiating a search for alternative approaches to PNC synthesis and film forming. Herein, fiber‐spinning chemistry (FSC) is proposed for easy‐to‐perform synthesis of highly stable PNC fibrous films. The FSC process utilizes spinning fibers as reactors, reducing the generation of VOCs. This method enables the fabrication of CsPbX(3) (X = Cl, Br, I) PNCs/poly(methyl methacrylate)/thermoplastic polyurethanes fibrous films at room temperature in one step, exhibiting tunable emission between 450 and 660 nm. Significantly, the in situ generation of PNCs in hydrophobic core–shell nanofibers results in highly improved fluorescence stability. PNCs/polymer fibrous films keep constant in photoluminescence (PL) after storage at atmosphere for 90 d and retain 82% PL after water immersion for 120 h (vs fluorescence quenching in 10 d in air or 5 h in water for pristine PNCs). The PNCs/polymer fibrous films endowed with superior optical stability and great flexibility show promising potentials in flexible optoelectronic applications. This work paves a facile way toward high‐performance nanoparticles/polymer fibrous films.