A combination of top-down (electrospinning for fabrication of high surface area micro/nanofibers) and bottom-up (creation of supramolecular structures through self-assembly processes in fiber) approaches has enabled the generation of conjugated polymer-embedded fibers. The efficiency of fiber formation, encapsulated with colorimetric, and fluorogenic conjugated polydiacetylene supramolecules, was dependent on electrospinning conditions, such as concentration, molecular weight, type of matrix polymer, and solvent. In general, electrospinning of a chloroform solution containing 1.6 wt.-% of a diacetylene monomer and 4 wt.-% PEO of molecular weight 300 000 g.mol(-1) followed by 254 nm UV irradiation resulted in clean formation of polydiacetylene-embedded fibers. In addition, UV irradiation during electrospinning can be used for in situ and continuous generation of polydiacetylenes-encapsulated fibers.