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Polyethylene terephthalate (PET) waste has become a major challenge for the conservation of the environment due to difficult degradation. For this reason, it is important to develop new recycling strategies for reusing this waste. In this work, the electrospinning technique was used to synthesize composite nanofibers of polyvinylpyrrolidone (PVP), recycling PET (RPET) that was obtained from the chemical recycling of postconsumer PET with glycolysis and styrene (ST) as a crosslinking agent. The polymer solutions were analyzed by viscosity and frequency sweeping, while the composite nanofibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis/differential scanning calorimetry (TGA/DSC), and nanoindentation to compare their properties. The PVP nanofibers presented an average diameter of 257 nm; the RPET/PVP and RPET/PVP/ST composite nanofibers had average diameters of 361 nm and 394 nm, respectively; and the modulus of elasticity and hardness of the RPET/PVP/ST composite nanofibers were 29 and 20 times larger, respectively, than those of the PVP nanofibers. With the synthesis of these composite nanofibers, a new approach to PET recycling is presented. [ABSTRACT FROM AUTHOR]