The structure of a cationic surfactant deposited from an evaporating thin film onto a hydrophilic, anionic substrate was investigated using atomic force microscopy (AFM) and imaging ellipsometry. A vertical substrate is receded from solution above a critical pulling speed, entraining a thin film on the substrate. The convective flow field near a contact line typical of sub-critical withdrawal is replaced by benign plug flow in the wedge-like film. Confinement of surfactant molecules in this constantly thinning film environment results in a non-trivial arrangement of molecules along the solid-liquid and liquid-vapor interfaces into island self-assemblies (typically ~ few µm in lateral extent) along the solid-vapor interface. AFM measurements show the heights of these assemblies are quantized in units consistent with the length of the surfactant molecule, beginning with a bilayer. Increasing the film residence time alters the distribution of these heights and eventually causes dewetting patterns devoid of islands to appear along the interface. Island coverage increases with pulling speed and soak time prior to recede, independent of film residence time. Switching the solute-substrate electrostatic interaction from attractive to repulsive by using an anionic surfactant does not inhibit island formation, proving this technique could potentially be used to deposit a wide range of molecules.