Acrylic acid monomer in a viscous supporting nylon solution was polymerized and fabricated simultaneously via an electrospinning process. This novel polymerization method defines the fiber morphology as a network of interconnected mats. This network consists of smaller poly(acrylic acid) (PAA) fibers, approximately 19 nm in diameter, and larger nylon 6 fibers, approximately 75 nm in diameter. These two different fibers are separated by extraction of PAA from the fibrous mat in water and differentiation of field-emission scanning electron microscopy (FESEM) images of the same mat using before and after extraction of PAA. The structure of the extracted PAA was confirmed by (1)H NMR and Fourier transform infrared (FT-IR) analysis. The observed modification to conventional electrospun mats is due to the presence of an extra phase-separated PAA produced by the electrospinning polymerization process. Finally, fiber morphologies and hybrid property were characterized via FT-IR, FESEM, thermogravimetric analysis, and X-ray diffraction. Similarly extracted samples and synthesis PAA were characterized in FT-IR and (1)H NMR spectroscopy.