Triaxial electrospinning is a novel method for fabrication of multilayered nano and microsize fibers with desirable features for particular applications. Since the effect of solvent volatilities in each layer and relative polymer molecular weights on uniform encapsulation of the core polymer process is not well understood, we evaluated (i) the role of solvent volatilities, and (ii) molecular weights using cellulose acetate (CA, 30 kDa), polycaprolactone (PCL, 45 kDa and 80 kDa), mineral oil, and polyvinyl alcohol (PVA, 30 kDa and 100 kDa). Different solvent mixtures were evaluated based on the boiling points determined using a simulator. Inner mineral oil was selectively removed to form Hollow fibers. Analysis of chemical compositions using FT-IR and DSC revealed the presence of each component. 24-h viability of human umbilical vein endothelial cells indicated the formed fibers were not toxic. Scanning electron micrographs indicated the formation of triaxial structured fiber of outer hydrophobic PCL/CA/Hollow, PCL/PVA/Hollow and outer hydrophilic CA/PCL/Hollow fibers. Tensile tests (both wet and dry) revealed that PCL/CA/Hollow fibers had increased stiffness and load carrying capacity than CA/PCL/Hollow fibers. Successful fiber formation was dependent on ensuring that the outer shell formed first i.e., the relative solvent volatility of encapsulating core polymer to lower than that of the shell polymer. (C) 2015 Elsevier B.V. All rights reserved.