Nano-fluid flooding is a new method capable of improving oil recovery; however, nanoparticles (NPs) significantly affect electric dehydration, which has rarely been investigated. The effect of silica (SiO2) NPs on the droplet–interface coalescence was investigated using a high-speed digital camera under an electric field. The droplet experienced a fall, coalescence, and secondary droplet formation. The results revealed that the oil–water interfacial tension and water conductivity changed because of the SiO2 NPs. The decrease of interfacial tension facilitated droplet deformation during the falling process. However, with the increase of particle concentration, the formed particle film inhibited the droplet deformation degree. Droplet and interface are connected by a liquid bridge during coalescence, and the NP concentration also resulted in the shape of this liquid bridge changing. The increase of NP concentration inhibited the horizontal contraction of the liquid bridge while promoting vertical collapse. As a result, it did not facilitate secondary droplet formation. Moreover, the droplet falling velocity decreased, while the rising velocity of the secondary droplet increased. Additionally, the inverse calculation of the force balance equation showed that the charge of the secondary droplet also increased. This is attributed to nanoparticle accumulation, which resulted in charge accumulation on the top of the droplet.