Standalone poly(vinyl alcohol) (PVA) nanowebs were developed in an environmentally friendly manner, and their breathability values were obtained. The strength of nanowebs was enhanced by heat cross-linking. Breathability values of untreated and heat cross-linked nanowebs remain the same indicating that stronger nanowebs can be developed without compromising its breathability. Transmission FTIR showed an increase in the crystallinity and no significant changes in the structure of PVA nanowebs after heat cross-linking. Stronger and breathable nanowebs can find broader applications such as tissue culture scaffolds, protective clothing liners, and air filters.