The interaction of methyl orange dye with a layered double hydroxide colloidal material is investigated using real-time polarization-resolved second-harmonic scattering (SHS). Interlayer charge compensating anion exchange is studied from initial carbonate or nitrate anions to methyl orange negatively charged dye. A theoretical model, taking into account the field retardation effect, is presented to simulate the polarization-resolved SHS experiments. Various geometrical dye configurations inside or around the host material have been modeled. A comparison with the experimental data permits to give a microscopic description of the dye organization and its time evolution during the intercalation process in the material.