Microfluidics for the preparation of double emulsion droplets for a wide range of applications in medicine, agronomy, and materials science. The requirements for droplet preparation vary in different fields, and these needs can be met by altering fluid parameters, microchannel geometries, and other means. Therefore, this paper explores the influence of microfluidic device geometry on double-emulsion droplet molding using a VOF approach. The influence of variations in the length between the inject tube of the inner phase and inlet of the collection tube, the outlet width, the angle between phases, and the outlet angle on the double-emulsion droplet formation distance as well as on the area and other parameters were emphasized. The results show that increasing the length between the inner phase injection tube and inlet of the collection tube helps to improve the stability of droplet formation; the change of the outlet width has less effect on droplet formation; and the change of the angle between the phases tends to lead to the shift of the droplet formation mode, which has a greater effect on droplet formation. This study can provide a reference for optimizing the microchannel structure.