We demonstrate herein the fabrication of novel multicompartmental biodegradable microstructures via electrohydrodynamic cospinning of two or more polymer solutions. Under optimized processing conditions, the interface between the solutions can be sustained continuously for long time intervals, yielding fibers with multiple chemically distinct compartments. Simultaneous control over internal fiber architecture and the spatial arrangement of individual compartments combined with precise long-range fiber alignment makes these fibers potential candidates for applications such as tissue engineering or cell culture studies.