The recently presented drop-on-demand (DOD) aerosol generator overcomes some of the drawbacks of pneumatic nebulization, as its aerosol is no longer generated by gas–liquid interaction. In the current study, an advanced imaging technique is presented, based on a CCD camera equipped with magnifying telecentric optics to allow for fast, automated and precise aerosol characterization as well as fundamental studies on the droplet generation processes by means of pseudo-cinematography. The DOD aerosol generator is thoroughly characterized regarding its droplet size distribution, which shows few distinct populations rather than a continuous distribution. Other important figures, such as the Sauter diameter (D3,2) of 22μm and the span of 0.4 were also determined. Additionally, the influence of the electrical operation conditions of the dosing device on the aerosol generation process is described. The number and volume of the generated droplets were found to be very reproducible and user-variable, e.g. from 17 to 27μm (D3,2), within a span of 0.07–0.89. The performances of different setups of the DOD as liquid sample introduction system in ICP-MS are correlated to the respective achievable aerosol characteristics and are also compared to the performance of a state-of-the-art μ-flow nebulizer (EnyaMist). The DOD system allowed for improved sensitivity, but slightly elevated signal noise and overall comparable limits of detection. The results are critically discussed and future directions are outlined. Further characterization of the drop-on-demand aerosol generator for sample introduction in atomic spectrometry. Display omitted •Significantly improved ICP-MS sensitivity using the DOD vs. EnyaMist.•Comparable detection limits but slightly worse short-term precision.•Superior flexibility compared with conventional/miniaturized pneumatic nebulizers.•Electrical operation conditions of the DOD influence aerosol characteristics.•The ejected volume can be adjusted from 8 to 36pL per dosing event.