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Electrospinning is a straightforward approach for efficiently creating continuous fibers within the submicron to nanometer size range. Electrospun fibers possess excellent properties like high porosity, large specific surface area, tunable morphology, small diameter, etc., making them desirable in various applications. Because of its various properties, polymer is one of the most used materials as the spinning solution in electrospinning. Electrospun polymeric fibers, by themselves, may serve limited applications. Therefore, they are usually mixed with other materials to serve many applications. There are many ways in which these other materials are mixed with polymers in electrospinning, like doping, surface treatment, functionalization, etc. There are several studies published that report on the various composite fibers produced using electrospinning. However, a review focused solely on the production of heterogeneous fibers, where the electrospun fibers are intrinsically made of more than one material, is lacking. Herein, we review different heterogeneous fibers synthesized using electrospinning and their fabrication methods.