Two analogous polyimides (PIs) containing flexible isopropylidene units were prepared. One was based on 4,4-oxydiphthalic anhydride and 4,4-(4,4-isopropylidenediphenyl-1,1-diyldioxy) dianiline and the other was based on 4,4-(4,4-isopropylidenediphenoxy) bis(phthalic anhydride) and bis(3-aminophenyl) methyl phosphine oxide. The ability of these two PIs to form uniform nanoscaled fibers was investigated by electrospinning technique. At optimal spinning conditions, PI fibers were electrospun onto the surface of woven poly(ethylene terephthalate) (PET) support to form a bilayer composite structure. These new fabric systems were analyzed regarding morphology, air permeability, wetting properties, and thermal stability. It was expected that the new PET/PI mats would possess enhanced properties compared with the initial woven PET fibers due to the excellent properties of PIs. Experimental results showed that PET woven substrate coated with electrospun PI fibers had improved values of air permeability, water contact angle and thermal stability when compared with the initial woven PET fibers.