Styrene droplets were generated using a coaxial flow droplet microfluidic device. In the self-assembled coaxial flow droplet generation device, styrene was used as the dispersed phase and the aqueous solution containing surfactant was used as the continuous phase to study the generation of styrene droplets. The effects of the two-phase flow rate and surfactant concentration on the droplet size were investigated, and a mathematical correlation formula for predicting the droplet size was obtained by three-dimensional analysis of the experimental values. The results showed that the diameter of the droplet was negatively correlated with the flow rate of the continuous phase and the concentration of surfactant in the continuous phase, and the diameter of the droplet was positively correlated with the flow rate of the dispersed phase. The diameter of styrene droplets produced by coaxial flow droplet generation device ranges from 70.39 μm to 377.09 μm. The predicted values obtained by the correlation formula are in good agreement with the experimental values, with an error within 25%. The successful generation of styrene droplets in the self-assembled coaxial flow device provides the idea for the generation of monodisperse Oil-in-Water droplets.