The primary aim of this study was to investigate the generation characteristics of organic solvent droplets with and without triglyceride oil by electrospraying using single-nozzle and nozzle-array devices. The liquids used were ethanol (10–99.5%), ethanol (99.5%) solutions containing a triacylglyceride oil, ethyl acetate, hexane, and heptane. The droplet generation behaviors from an electrode nozzle were observed using high-speed video cameras. Unstable micro-dripping mode was observed when using ethanol (<50%), hexane, and heptane. In contrast, the stable electrospraying by cone-jet mode was achieved when using ethanol (>66.7%) and ethyl acetate. The jet diameter values mostly ranged between 10 and 20μm, which is similar to the estimated ones. High-speed photographic observation at a frame rate of 106s−1 demonstrated the generation of ethanol droplets at very high frequencies of 3.0×105–5.0×105s−1 by breaking up the jet. The ethanol jet diameter increased with increasing the flow rate (1–10mL/h). The nozzle number per device did not affect the jet diameter when the flow rate per nozzle is the same. The stable cone-jet mode was also achieved when using ethanol solution containing 0.1% triacylglyceride oil. Triacylglyceride oil droplets with diameters of about 2μm were collected after evaporating ethanol from the droplets generated by electrospraying.