Ionically self-assembled monolayers (ISAMs) have recently been shown to spontaneously exhibit a polar ordering that gives rise to a substantial second order nonlinear optical (NLO) response. Here, the deposition of ISAMs has been studied in situ via second harmonic generation (SHG). We show that the adsorption and ordering of a noncentrosymmetric nonlinear optical polymer is constant over a wide range of concentrations. Upon immersion in the NLO-active polyelectrolyte solution, the SHG rises sharply over the first minute. Immersion in the NLO-inactive partner polyelectrolyte leads to a reduction in the SHG signal. Furthermore, when the film is removed from the NLO-active solution and allowed to dry, the SHG increases rapidly as the water evaporates. These studies provide greater understanding of the processes by which noncentrosymmetric order is formed in ISAM films and allows design of improved self- assembled nonlinear optical materials.