The development of stable vesicular assemblies and the understanding of their interaction and dynamics in aqueous solution are long-standing topics in the research of chemistry and biology. Fatty acids are known to form vesicle structure in aqueous solution depending on the pH of the medium. Protic ionic liquid of fatty acid with ethyl amine (oleate ethyl amine, OEA) as a component spontaneously forms a vesicle in aqueous solution. The general comparison of dynamics and interaction of these two vesicles have been drawn using fluorescence correlation spectroscopy (FCS) and fluorescence lifetime imaging microscopy (FLIM) measurements. Further, FLIM images of a single vesicle are taken at multiple wavelengths, and the solvation of the probe molecules has been observed from the multiwavelength FLIM images. The lifetime of the probe molecule in OEA vesicle is higher than that in simple fatty acid vesicles. Therefore, it suggests that the membrane of the OEA vesicle is more dehydrated compared to that of fatty acid vesicles, and it facilitates OEA vesicles to fuse themselves in the presence of electrolyte, sodium chloride (NaCl). However, under the same conditions, only fatty acid vesicles do not fuse. The fusion of OEA vesicles is successfully demonstrated by the time scan FLIM measurements. The different events in the fusion process are analyzed in the light of the reported model of vesicle fusion. Finally, the local viscosity of the water pool of the vesicle is determined using kiton red, as a molecular rotor. With addition of NaCI, the fluidity in the interior of the vesicle is increased which leads to disassembly of vesicle. The rich dynamic properties of this vesicular assembly and the FLIM based approach of vesicle fusion will provide better insight into the growth of a protocell membrane.