We herein report the preparation and properties of the first polymer blend using pyrene functionalized polyaniline (pf-PANI). The pf-PANI has been synthesized and its blend has been prepared with the copolymer of vinylidene fluoride and hexafluoropropylene P(VDF-HFP). The FTIR results reveal intermolecular interaction between the polar amide group of pf-PANI and the polarized CH2 group of P(VDF-HFP). The crystalline phase of PVDF of the copolymer revealed a transformation from α to β crystalline form after blending with pf-PANI, as found from FTIR and XRD measurements. The calorimetric measurements together with DMA results revealed the blend is partially miscible. The SEM measurements showed that the pf-PANI has been dispersed uniformly in the P(VDF-HFP) matrix. The solution photoluminescence spectrum of the pf-PANI exhibited emission in the purple–blue region and is slightly red shifted for the blend. The possible applications of this flexible fluorescent pf-PANI/P(VDF-HFP) has been suggested. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40162.