. High-resolution tapping-mode atomic force microscopy (AFM) and near-field scanning optical microscopy (NSOM) are used to study nonstoichiometric polyelectrolyte-surfactant complexes (PSCs) formed between poly(vinyl sulfate) and alkyltrimethylammonium bromide (C(n)TAB). The morphological evolution of PSC films prepared with different surfactant loadings (i.e., different surfactant/anionic-site stoichiometries) is explored as a function of surfactant chain length (n = 12, 14, 16, 18). PSC films were prepared with 1%, 10%, 25%, and 50% surfactant loading. At the lowest loading, relatively uniform films are obtained, despite the fact that the surfactant concentrations in the solutions employed were all above the critical aggregation concentration. At 10% loading, for the longer chain surfactants (n = 16 and 18), small protrusions (10-40 nm in height) appear in the films. These are attributed to the formation of spheroidal and/or discoidal polyelectrolyte-surfactant micelles. For films of 25-50% surfactant loading, lamellar PSC bilayer domains are clearly observed for all but those prepared with C(12)TAB. In many samples, both micellar structures and lamellar phases are found, indicative of the complicated morphological,attributes of these materials. Evidence for surfactant-dependent dewetting of the glass substrate surface is also obtained. Fluorescence NSOM images of dye-doped versions of the PSCs provide additional proof for the film structural assignments. AFM images of the lamellar structures at 50% surfactant loading show the presence of interesting defected bilayer regions. The possible origins of these defected regions and their associated bilayer height variations are discussed.