Herein we demonstrate the ability to fabricate polymeric microtubes with an inner diameter of approximately 3 microm through co-electrospinning of core and shell polymeric solutions. The mechanism by which the core/shell structure is transformed into hollow fibers (microtubes) is primarily based on the evaporation of the core solution through the shell and is described here in detail. Additionally, we present the filling of these microtubes, thus demonstrating their possible use in microfluidics. We also report the incorporation of a protein (green fluorescent protein) within such fibers, which is of interest for sensorics.