The aerial atomizer is the most essential component of the plant protection UAV (unmanned aerial vehicle). However, the structural optimization of existing aerial atomizers lacks comprehensive consideration of spray parameters and structural parameters, and there is a shortage of available atomizer spray models, resulting in the unstable effect of UAV application. In our previous work, an aerial dual-atomization centrifugal atomizer was developed. In order to obtain an aerial atomizer with good atomization effect and its atomization model, structural optimization at different rotation speeds and flow rates of the atomizer, and its atomization performance, are studied in this paper. Firstly, with the droplet volume median diameter (VMD) and spectral width (SRW) as the evaluation index, through the single-factor, Plackett–Burman and Box–Behnken tests, the influence of rotation speed, flow rate, tooth number and tooth shape were studied. The regression models of the droplet VMD and SRW were established using multiple quadratic regression fitting of the test data. Secondly, in order to achieve the lowest droplet VMD and SRW, the response surface method and post-hoc multiple comparison method were used to obtain the optimized structure of the atomizer’s rotation ring at different rotation speeds (600–7000 r/min) and flow rates (500–1000 mL/min). Lastly, with the effective swath width (ESW) of the optimized atomizer as the evaluation index, through the Box–Behnken test, the influence of rotation speed, flow rate and spray height were studied. The multiple quadratic regression model of ESW was established with the test data. The test results indicated that rotation speed, flow rate and tooth number had a significant effect on droplet VMD and SRW; tooth shape had no significant effect on the droplet VMD and SRW, however, the square tooth shape had the best atomization effect; and rotation speed, flow rate and spray height had a significant effect on ESW. The optimized structural parameters were tooth shape: square, and tooth number: 20. The determination coefficient R2 of the regression model of VMD, SRW and ESW were 0.9976, 0.9770 and 0.9974, respectively, which indicates that the model was accurate, and can evaluate and predict the spray effect. This paper provides an optimized dual-atomization centrifugal atomizer, and its regression models of VMD, SRW and ESW for UAV applications can provide a reference for efficient UAV spraying.