Electrohydrodynamic (EHD) spraying is an interesting phenomenon where the liquid subjected to an electrical stress deforms into an electrified liquid drop, a thin liquid jet, or the so-called Taylor cone, which is also highly complicated owing to its various spraying modes and behaviors. Due to the lack of critical information such as the electric charge density and internal velocity profile, the underlying physics behind the transition of different EHD spraying modes are still not adequately understood. In light of this, we conducted a numerical investigation into the transition of EHD spraying modes and behaviors under the three most important operating parameters including electric voltage, nozzle height, and liquid flow rate. Four typical spraying modes, namely, dripping, cone-jet, multi-jet, and jetting, are observed. From the numerical results, we obtained the voltage distribution in the environment, electric charge density at the liquid–air interface, and velocity profile inside the liquid, which help us to comprehensively analyze and explicate the influences of these three parameters on the transition of spraying modes and behaviors. This eventually leads us to a spraying mode map showing the correlation between the spraying modes and the electric Bond number. To the best of our knowledge, this is the first numerical work focusing on the transition of EHD spraying mode, from which we intend to expand the knowledge of this interesting phenomenon.