A single step method for encapsulation of clinically relevant proteins viz., Bovine Serum Albumin (BSA), Lysozyme and Insulin molecules, inside core-sheath structured polymer fibres using coaxial electrospinning technique, is described. Transmission electron microscopic pictures show the formation of core-sheath structure. The secondary structure of the proteins was characterized through CD spectroscopy. The secondary conformation was retained with a minor decrease in β-conformation and an increase in the random and turn conformations after coaxial electrospinning. This method of encapsulation is simple and requires little or no harsh treatment of sensitive biomolecules like insulin. Thus, the core-sheath structure of the fibres might apparently help protect the biomolecules during and after electrospinning, in addition to providing a high interactive surface area for controlled release. This scheme will be suitable for applications in cell culture and tissue regeneration. © 2013 American Scientific Publishers, All rights reserved.