This paper is an experimental study on the optimal operating conditions of direct charging type electrospray for particulate matter collection. To perform the research, a direct charging type electrospray visualization system was configured to photograph the spray shape of microdroplets, and experiments were performed with varying electrode distance, flow rate, and applied voltage, which are the main factors affecting the particulate matter collection efficacy. Through image processing, the total number of microdroplets according to each condition was analyzed, and the number of microdroplets with a diameter of 1.5 mm or less was confirmed. In addition, by calculating the number of microdroplets per power consumption according to the applied voltage, the optimal operating conditions were derived in terms of energy consumption efficacy, and the microdroplet size distribution was analyzed under the optimal operating conditions. As a result of the experiment, it was confirmed that the optimal operating condition was at a flow rate of 10 mL/min and a voltage of -20 kV in case of 5 mm electrode distance, and at a flow rate of 15 mL/min and a voltage of -30 kV in case of 100 mm electrode distance.