In this work, the optimal electrospinning conditions of trans-polyisoprene (TPI) solutions were evaluated nevertheless its lower glass transition temperature than the room temperature. Subsequently, chemical crosslinking of TPI nonwovens was firstly investigated by vulcanizing at high temperatures in the case of the persistence of nanofiber structure. For this purpose, curing agents of TPI were embedded in TPI nanofibers by co-electrospinning, and then a protect layer was coated on TPI nanofibers by filtering gelatin solution going through TPI nonwoven before the vulcanization at 140-160 A degrees C. The results showed that the vulcanization of TPI fibrous nonwoven at high temperatures did not destroy the fiber morphology. Interestingly, TPI fibrous nonwovens after vulcanization showed excellent mechanical properties (similar to 17 MPa of tensile strength) that could be comparable to or even higher than that of some bulk rubber materials.