Ultraviolet absorption spectrophotometry was applied to the determination of sodium lauryl diphenyl ether disulfonate (SLDED) in SLDED and sodium dodecyl sulfonate (SDS) complex systems. The results indicated that the existence of SDS not only can improve the ultraviolet absorption intensity of SLDED but also can greatly decrease the apparent critical micelle concentration values of SLDED in aqueous solution. With the addition of 0.500 mmol·L-1 SDS, the ultraviolet absorption intensity of SLDED increased from 0.631 to 0.682, with an increase of 8.1%. In addition, the apparent critical micelle concentration values of SLDED reduced from 1.12 to 0.702 mmol·L-1 when the concentrations of SDS respectively increased from 0 to 0.500 mmol·L-1. The results also showed that the interference of SDS on the ultraviolet absorption intensity of SLDED could be greatly reduced by HP-β-CD. With the addition of 1.000 mmol·L-1 HP-β-CD, the ultraviolet absorption intensity of 0.500 mmol·L-1 SLDED increased from 0.796 to 0.798, with an increase of only 0.3%, much lower than the increase without HP-β-CD. SLDED molecules were more likely to form inclusion complexes with HP-β-CD rather than micelles. Thus, the standard molar Gibbs free energy for SLDED from aqueous SDS/SLDED binary blend solution to the micelle, ΔγGθm, was respectively increased from -41.098 to -39.833 kJ·mol-1, -39.488 and -38.184 kJ·mol-1 while the concentrations of HP-β-CD increased from 0 to 0.400, 0.800 and 1.200 mmol·L-1. The results of Job’s plot for inclusion complexation of SLDED with HP-β-CD indicated that “HP-β-CD/SLDED” inclusion might be formed with the molar ratio of 2∶1. The concentration of SLDED in aqueous SDS/SLDED binary blend solution, could be accurately calculated by adding HP-β-CD with the molar ratio of 2∶1, and the recovery rate of SLDED was 100.8%~101.4%. The results of 1H-NMR and FT-IR exhibited that the interference of SDS on determination of SLDED could be greatly reduced because of the formation of SLDED/HP-β-CD inclusion with SLDED molecule locating within the HP-β-CD molecule.