Insight into plasma dynamics under usual pulsed laser deposition (PLD) conditions for NiO thin film growth is provided by implementing angle- and time-resolved Langmuir probe (LP) methods. The selective separation generated an acceleration region that separates ions based on nature and ionisation state. A maximum of the kinetic energy for most plasma components was found for 0.5–2 Pa Ar, while the time-resolved analysis revealed a multipeak evolution of the electron temperature, which widened and shifted with increasing pressure. Evidence of two temperature structures for NiO plasma is presented, and the estimation of the accelerating field generated between the two plasma structures reveals selective in acceleration in the first microsecond. The acceleration field has a maximum value for the O2 atmosphere at approximately 2 Pa, which shows the separation between drift-dominated kinetics and reaction-based dynamics. Further investigation in this 2 Pa region revealed the appearance of a perturbation consistent with the formation of a plasma fireball on the probe. The dynamics of these perturbations is affected by the nature of the gas having different incubation times.