Solution-, melt-, and co-axial electrospinning are well-known methods for producing nano- and microfibers. The electrospinning of colloids (or colloid-electrospinning) is a new field that offers the possibility to elaborate multicompartment nanomaterials. However, the presence of colloids in the electrospinning feed further complicates theoretical predictions in a system that is dependent on chemical, physical, and process parameters. Herein, we give a summary of recent important results and discuss the perspectives of electrospinning of colloids for the synthesis and characterization of multicompartment fibers.