Eu3+-doped polystyrene and polyvinylidene fluoride (PVDF/Eu3+ and PS/Eu3+) nanofibers were made using electrospinning. These fibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), energy dispersive spectroscopy (EDX) and photoluminescence (PL). Spectral analysis of PVDF/Eu3+ and PS/Eu3+ nanofibers was based on their emission spectra. A bright red emission was noticed from Eu3+ that was assigned to the hypersensitive (D0F2)-D-5-F-7 transition. The enhanced intensity ratios of (D0F2)-D-5-F-7 to (D0F1)-D-5-F-7 transitions in the nanofibers indicated a more polarized chemical environment for the Eu3+ ions and greater hypersensitivity for the (D0F2)-D-5-F-7 transition, which showed the potential for application in various polymer optoelectronic devices. The Eu3+-doped polymer (PVDF/Eu3+ and PS/Eu3+) nanofibers are suitable for the photoluminescent white light fabric design of smart textiles. This paper focuses on the potential application of smart fabrics to address challenges in human life.