The complexation of cetyltrimethylammonium bromide (CTAB) with sodium dodecyl sulfate (SDS) with sodium dodecyl benzene sulfonate (SDBS), with tetraiodophenolsulfonphthalein (TIPST) as a spectral substitute was investigated at pH 5.89 and 8.30 by the microsurface adsorption—spectral correction (MSASC) technique. The aggregations of TIPST, SDS, and SDBS on CTAB obeyed the Langmuir isothermal adsorption. The aggregates TIPST–CTAB, TIPST 2 –CTAB 3 , SDS 3 –CTAB 2 , and SDBS 3 –CTAB 2 were formed at 20 °C and the binding constants of all the aggregates were determined. The replacement of TIPST-binding CTAB monomer with SDS or SDBS at pH 5.89 was applied to the quantitative determination of anionic detergent (AD) in water with satisfactory recovery.