Herein, the movement of two non-centric droplets in hexane was studied using a molecular dynamics method to understand the microscopic coalescence mechanism of droplets with an initial velocity in an electric field. Unlike previous studies, this study overcame the limitations in experimental conditions and conventional analytical tools to understand the mechanism of droplet coalescence under the coupling effect of electric and velocity fields at the molecular level. This has implications for the development of inkjet printing technology and microfluidics. The analysis of droplet trajectories and centroid distances revealed that the Weber number can be divided into three ranges according to the three modes of droplet behaviour: incomplete coalescence, complete coalescence and non-coalescence. At a low Weber number (We < 1), the inhomogeneous distribution of ions in droplets causes the fragmentation of droplets that are not completely coalesced. The interaction energy and weak interaction analysis shows that hydrogen bonds between water molecules are the strongest, followed by van der Waals interactions, which is very prominent in the first and second coordination layers. Hexane and water molecules exhibit van der Waals interactions. As the Weber number increases from 0 to 5, the total interaction energy between two droplets increases, and the number of hydrogen bonds increases. A decrease in the total interaction energy, number of hydrogen bonds, radial distribution function and coordination number in a single droplet shows that increasing the Weber number loosens the single droplet and simultaneously promotes the coalescence of two droplets. However, when We > 5, the total interaction energy and number of hydrogen bonds between droplets are zero, and the two droplets do not merge. This is because the angle between the electric field and centreline of the droplets is so large that the electric field cannot horizontally act upon the droplets. This study provides a fundamental guide for studying the mechanism of droplet coalescence under the coupling effect of electric and flow fields.