Electrospraying can be performed in both liquid and air media. We have found that electrospraying in insulating liquids is more stable under a wide range of applied voltages compared to that in air. The stability of the spray in insulating materials indicates a significant relationship between electrical interaction and spray stability within liquid media. The electrospray in air diminished with an increase in the applied voltage from 3 to +4 kV, while that in n-hexane generated a fine spray even at applied voltages exceeding +9 kV. The absence of corona discharge in a spray nozzle immersed in liquid n-hexane contributed to achieving a stable electrospray process with a narrow size distribution. However, in air, voltage-induced corona discharge caused by the ionization of atmospheric molecules (such as N2 and O2) led to a decrease in the stability of the electrospray. To elucidate the differences between the dynamic processes of electrospraying in air and n-hexane, we conducted measurements using high-speed camera imaging, analyzed the size distribution of charged droplets, and assessed circuit current.