In this study, Acid Soluble Collagen-g-P(methyl methacrylate-co-ethyl acrylate) (CME) was synthesized to take advantage of the flexibility of the resulted branched polymer chains and the high density of their chain entanglement. The coaxial electrospinning technique was applied to study the effect of electrically and structurally varied materials on fiber formation and fiber morphology when CME and Nylon 66 were electrospun as core and shell respectively. By tailoring the electrostatic field, different fiber content was achieved. The effect of chain orientation and intermolecular forces between the polymeric chains was investigated in the formed fibers by measuring thermal and mechanical properties, hydration degree and degradability. This approach to in situ fiber formation is not restricted to biomedical but has potential end-uses in a variety of multi-functional applications.