In this study, we have presented the microscopic behavior of water-in-oil nanodroplet and its disintegration in the presence and absence of tbp amphiphile. Our findings reveal that tbp adsorbs at the water droplet surface, forming a layered structure, which increases the surface area and curvature compared to pure nanodroplets without amphiphile. The adsorbed tbp enhances the surface heterogeneity of the nanodroplet, disrupting the water structure and leading to the disintegration of the nanodroplet into smaller water clusters, a process that accelerates linearly with increasing temperature. We also observed that interfacial tbp facilitates the transport of interfacial water to the organic phase by forming surface-specific morphological features known as protrusions. These protrusions resemble the morphologies observed in solvent extraction systems that mediate the transport of ion pairs from the aqueous to the oil phase. The insights provided by this study may assist experimentalists in understanding the microscopic behavior of water-in-oil nanodroplets and the mechanism of liquid/liquid extraction in the presence of amphiphiles.