In this manuscript, the application of cetyltrimethylammonium bromide (CTAB) and cetylpyridinium chloride (CPC) for the removal of Naphthol Green B (NGB) as a synthetic effluent has been studied. The solubilization of NGB by a single and mixed micellar system using Triton X-100 (TX-100) as a nonionic surfactant has been performed to establish both the extent of the partitioning (kx) of NGB and ultimately their respective Gibbs free energies ΔGp as well. An applied methodology, micellar-enhanced ultrafiltration (MEUF), has also been studied in different micellar media of cationic surfactants by variation in some selective parameters, such as the concentration of surfactant, electrolyte, pressure, pH, and RPM to obtain optimum conditions. The results have been analyzed by a UV/visible double beam spectrophotometer. ΔGp was found to be −39.65 kJ/mol and −47.94 kJ/mol by CTAB and CPC, respectively, in the presence of a nonionic surfactant. The maximum value of Gibbs free energy (ΔGp) of the partition was obtained by CPC. The values of the rejection coefficient (R%) and permeate flux (J) are also calculated. A maximum removal of 99.77% and 98.53% by CTAB and CPC, respectively, was obtained. It has been observed that both of the surfactants are strong candidates for NGB removal.