Pyrolysis of methyl ricinoleate (MR) can produce undecylenic acid methyl ester and heptanal which are important chemicals. Atomization feeding favors the heat exchange in the pyrolysis process and hence increases the product yield. Herein, predictive models to characterize the atomization process were developed. The effect of spray distance on Sauter mean diameter (SMD) of atomized MR droplets was examined, with the optimal spray distance to be 40–50 mm. Temperature mainly affected the physical properties of feedstock, with smaller droplet size obtained at increasing temperature. In addition, pressure had significant influence on SMD and higher pressure resulted in smaller atomized droplets. Then, a model for SMD prediction, combining temperature, pressure, spray distance, and structural parameters of nozzle, was developed through dimensionless analysis. The results showed that SMD was a power function of Reynolds number (Re), Ohnesorge number (Oh), and the ratio of spray distance to diameter of swirl chamber in the nozzle (H/dsc), with the exponents of − 1.6618, − 1.3205 and 0.1038, respectively. The experimental measured SMD was in good agreement with the calculated values, with the error within ± 15%. Moreover, the droplet size distribution was studied by establishing the relationship between the standard deviation of droplet size and SMD. This study could provide reference to the regulation and optimization of the atomization process in MR pyrolysis.