The work investigates the correlation between the plasma characteristics and reactive chemical species generation in an Ar-nonthermal atmospheric pressure plasma-jet (Ar-NTAPPJ) under various operating conditions such as gas flow rate, excitation voltage, and electrode gap and demonstrates the application of such understanding in developing efficient nonthermal plasma systems. The critical plasma parameters such as electron temperature (T
e) and electron density (n
e) under the various operating conditions were estimated using optical emission spectroscopy coupled with the collision radiative model and Stark broadening methods. At optimal setting of 5 LPM gas flow rate, 4 kV excitation voltage, and 6 mm electrode gap resulted in maximum T
e (0.6 eV), enhancing •OH production (0.056 mM) in the liquid phase and OH(A-X) emission in the gas phase, highlighting the significance of operating conditions on building energy efficient plasma systems. The enhanced performance of the optimized Ar-NTAPPJ is demonstrated by taking atrazine as a model herbicide. The degradation performance data was correlated and validated with results obtained from spectroscopic diagnostics. By adequately tuning the operating parameters, four times enhancement in energy yield (∼150 mg kWh−1) was obtained without perturbing the nonthermal plasma mode. In nonthermal mode, to best of the authors knowledge, it is the highest reported energy yield for atrazine degradation. The scalability aspect of the present plasma jet was also investigated by Intensified Charge-Coupled Device camera-based imaging technique. The study establishes the importance of adequate diagnostics in developing efficient next-generation plasma reactors.