Engineering novel material structures has continually been pursued to further advance modern technologies. These advancements often rely on novel processing technologies. Although many processing parameters have been thoroughly examined in the field of electrospinning, the quasi-steady-state jetting modes are an exception. In this work, we examine the unique structures of polymer particles embedded in water-soluble electrospun fibers, which were successfully prepared via multi-nozzle electrospinning in a pulsating instability mode, without additional emulsifying steps. The aspect ratio of polymer particles can be tailored, based on the concentration of the inner solution, the size of the inner nozzle, and the conductivity of the solution. After dissolving the water-soluble sheath, the polymer particles can easily be dispersed in water and separated from the matrix. This novel electrospinning technology has the potential to open new areas of research such as electrohydrodynamic jetting for drug-delivery systems, sensors, scaffolds, and intelligent coatings.