Lipopeptides are an important group of biosurfactants expressed by microorganisms. Because they are well-known for being biocompatible, biodegradable, and highly surface active, they are attractive for a wide range of applications. Natural lipopeptide surfactants are however impure; it is hence difficult to use them for exploring the structure-function relation. In this work, a series of cationic lipopeptide surfactants, C(14)K(n) (n = 1-4), where C denotes the myristic acyl chain and K denotes lysine (Lys), have been synthesized, and their interfacial behavior has been characterized by studying their adsorption at the silicon/water interface (bearing a thin native oxide layer) using spectroscopic ellipsometry and neutron reflection (NR). The dynamic adsorption was marked by an initial fast step within the first 2-3 min followed by a slow molecular relaxation process over the subsequent 20-30 min. The initial rate of time-dependent adsorption and the equilibrated adsorbed amount showed a steady decrease with increasing n, indicating the impact of the molecular size, structure, and charge. NR revealed the formation of sandwiched bilayers from C(14)K(n), similar to conventional surfactants such as nonionic C(12)E(6) and cationic C(16)TAB. However, the electrostatic attraction between K and the silica surface caused confinement of the K groups, forcing the head segments into a predominantly flat-on conformation. This characteristic structural feature was confirmed by the almost constant thickness of the headgroup regions ranging from 8 to 11 Å as determined from NR combined with partial deuterium labeling to the acyl tail. An increase in area per molecular pair with n resulted directly from increasing the footprint. As a result, the hydrophobic back-to-back tail mixing and acyl chain tilting rose with n. The extent of chain-head intermixing became so intensified that the C(14)K(4) bilayer could be approximated to a uniform layer distribution.