To develop a novel functional composite material for textile application, a coaxial electrospinning technique was investigated to electrospin two different polymer solutions into core-shell structured nanofibers in which polyurethane and polycarbonate were used as core and shell materials, respectively. The resultant nanofibers were subsequently characterized by means of scanning electron microscope, transmission electron microscopy, fourier transform infrared spectroscopy, and tensile mechanical test. Furthermore, water vapour transmission rate and pliability of the resulting nonwoven mats were also measured. The preliminary results indicated that it is feasible to attach composite nanofibers, with possible fictionalization on the shell material, onto a substrate fabric.