Polyvinyl alcohol (PVA) nanofibers and single-walled carbon nanotube (SWNT)/PVA composite nanofibers have been produced by electrospinning. An apparent increase in the PVA crystallinity with a concomitant change in its main crystalline phase and a reduction in the crystalline domain size were observed in the SWNT/PVA composite nanofibers, indicating the occurrence of a SWNT-induced nucleation crystallization of the PVA phase. Both the pure PVA and SWNT/PVA composite nanofibers were subjected to the following post-electrospinning treatments: (i) soaking in methanol to increase the PVA crystallinity, and (ii) cross-linking with glutaric dialdehyde to control the PVA morphology. Effects of the PVA morphology on the tensile properties of the resultant electrospun nanofibers were examined. Dynamic mechanical thermal analyses of both pure PVA and SWNT/PVA composite electrospun nanofibers indicated that SWNT–polymer interaction facilitated the formation of crystalline domains, which can be further enhanced by soaking the nanofiber in methanol and/or cross-linking the polymer with glutaric dialdehyde.