© 2014 American Chemical Society. Single-walled carbon nanotubes (SWNTs) have been exfoliated in a poly(vinyl alcohol) (PVA) matrix using electrospinning. Raman features of SWNTs with single chirality were studied systematically in terms of the band frequency, intensity, and full width at half-maximum (fwhm). Polarized Raman spectroscopy was used to investigate the orientation of SWNTs, and it was found they were highly aligned along the fiber axis. The response of the nanotube G′-band to external strain for SWNT has been found to be dependent on the nanotube chirality, which suggests nonuniform efficiency of mechanical reinforcement for different nanotube species. The preparation and characterization methods demonstrated in this study have led to a better understanding of the effects of aggregation state, chirality, and external strain on the properties of nanotubes that are incorporated in a polymer matrix.