Strongly adsorbing polymer/surfactant (P/S) combinations have been proposed for long-term applications such as emulsion stabilization. However, P/S systems are known to exhibit nonequilibrium behavior despite steady-state surface characteristics. This work examines the coadsorption of dodecyltrimethylammonium bromide and sodium poly(styrene sulfonate) (PSS) using oil/water tensiometry, UV absorption, and vibrational sum frequency spectroscopy. To determine which features do not represent true equilibrium, the molecular details of PSS adsorption are compared for fresh and aged samples. At surfactant concentrations concurrent with bulk precipitation, significant differences between fresh and aged samples indicate that the strong initial coadsorption within this system is a nonequilibrium feature. We conclude that the long equilibration timescales arise from the slow assembly of non-adsorbing polyelectrolyte/micelle complexes below the critical micelle concentration. This study resolves a recent debate regarding system equilibria of surface-active P/S combinations at a water surface.