The structures of interfacial layers formed from mixtures of comb polymers, comprising a high charge density cationic backbone and poly(ethylene oxide) (PEO) side-chains, with the anionic surfactant sodium dodecyl sulfate (SDS) at the silica/water interface, have been determined using neutron reflectivity measurements. The use of mixtures in which only the isotopic composition of the surfactant is changed has made it possible to determine the interfacial volume fraction profiles for both the polymer and the surfactant. For the polymer with 90% of the segments charged and 10% of the segments carrying PEO side-chains, there are four regimes of interfacial behavior with increasing surfactant composition of the bulk solution. First there is adsorption of surfactant to the polymer-covered surface, then, slightly above polymer charge stoichiometry, there is adsorption of near-neutral polymer/surfactant complexes followed by the adsorption of polymer/surfactant aggregates, with a well-defined internal structure. If the concentration of SDS is increased directly from below polymer charge stoichiometry to above the cmc, micelles or polymer/micelle complexes interact with the pre-existing polymer layer. Increasing the fraction of segments carrying PEO side-chains to 25% suppresses the formation of charge-neutral polymer/surfactant complexes at the interface. There is an increase in the adsorption of surfactant, which interacts with the pre-existing layer of polymers. This results in the surface aggregation of SDS and a swelling of the PEO side-chains from a mushroom to a brush-like configuration.