Over the last decade, Lipid NanoCapsules (LNCs) have been intensively used as effective drug delivery systems; they are classically prepared using a phase-inversion method. Following formulation of the LNCs, the molecular insertion of commercially-available disteraoylphosphatidylethanolamine-peg amphiphiles is performed into the LNC shell, using a post-insertion method, more classically applied with liposomes. The subsequent LNC interfacial modifications are investigated by using size and electrokinetic measurements. More particularly, the length and the nature of the hydrophilic part of the post-inserted surfactant are modified. The results are discussed in order to improve our understanding of post-insertion mechanisms.