Abstract The high demand for light‐emitting and display devices made luminescent organic materials as attractive candidates. Solvent‐free organic liquids are one of the promising emitters among them due to the salient features. However, the inherent limitations of forming sticky and noncurable surfaces must be addressed to become an alternate emitter for large‐area device applications. Herein, we functionalized solvent‐free organic liquids having monomeric emission in bulk with polymerizable groups to improve the processability. The polymerizable group on carbazole, naphthalene monoimide, and diketopyrrolopyrrole‐based solvent‐free liquid emitters enabled on‐surface polymerization. These emitters alone and in combinations can be directly coated on a glass substrate without the help of solvents. Subsequent photo or thermal polymerization leads to stable, non‐sticky, flexible, foldable, and free‐standing large‐area films with reasonably high quantum yield. Our demonstration of the tunable and white light‐emitting films using polymerizable solvent‐free liquids might be a potential candidate in flexible/foldable/stretchable electronics. The new concept of polymerizable liquid can be extended to other functional features suitable for futuristic applications.
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