This study investigates the structural and physical properties of electrospun nanofibers (NF) produced from postconsumer poly(ethylene terephthalate) (PET) textile sources, including a no-dye polyester fabric, a 50/50 (by weight) mixture of red-and blue-dye polyester fabric, a polyester t-shirt, and from a postconsumer PET bottle. The postconsumer PET sources and their corresponding electrospun NF exhibited similar chemical structures and melting points. However, the electrospun PET NF showed distinct cold crystallization and sharper melt-crystallization behavior during rapid cooling as well as improved resolution of their Fourier transform infrared spectra. We hypothesize that this behavior can be attributed to the presence of locally ordered mesophases in the electrospun PET NF caused by rapid stretching of the electrically charged jet during electrospinning. The electrospun NF were found to be more amorphous, to have a lower degree of crystallinity, and to exhibit weakened signals of the trans conformers of the glycol units, when compared to their original postconsumer PET sources. Polyester-textile NF showed smaller average fiber diameters, higher degrees of crystallinity, higher melt-crystallization temperatures, and more rigidity than those of NF produced from PET bottles. The electrospun NF acquired from postconsumer PET textiles and bottles may hold promise as a versatile material for filtration, protective clothing, and environmental remediation.