Per- and polyfluoroalkyl substances (PFASs) are persistent micropollutants whose carbon–fluorine bonds resist conventional advanced oxidation. Nonthermal plasmas have emerged as a promising option for PFAS degradation, but the relative contributions of reactive oxygen species (ROS) and electrons are still being investigated. Herein, we compared sinusoidal alternating-current (AC) and nanosecond-pulsed discharges―in an identical plasma reactor with the same input power (30 W)―through diagnostics including voltage–current characterization, optical emission spectroscopy with vibrational and rotational temperatures and Hα Stark broadening for electron density, and aqueous H₂O₂ quantification. AC discharges produced more aqueous H₂O₂, stronger ·OH emission, and higher vibrational and rotational temperatures, yet showed lower perfluorooctanoic acid (PFOA) removal (85% ± 2%) and lower defluorination (61% ± 1%) than the pulsed discharge (96% ± 2% and 80% ± 2%, respectively). Among the diagnostics examined, electron density tracked the removal trend, being higher under pulsed operation (1.2 × 10¹⁶ vs. 8.3 × 10¹⁵ under AC operation). A pseudo-first-order kinetic model based on electron density qualitatively reproduced the observed PFOA decay rate, suggesting that the waveform may serve as a design variable for tuning electron and ROS-mediated pathways in plasma–water reactors.