Abstract The diffusion behavior of dihydroxybenzenes which can indicate their interactions with DTAB has been investigated by measuring the diffusion coefficients of dihydroxybenzenes in DTAB solutions. From the diffusion coefficient we can see that the position of the substituted hydroxyl groups can affect the interaction mechanism. Catechol mainly interacts with DTAB micelles by hydrophobic forces. However, hydroquinone mainly interacts with DTAB monomers rather than DTAB micelles through electrostatic forces. On the other hand, the interaction mechanism is also dependent on the hydrocarbon chain length. Shorter hydrocarbon chains interact much easier with dihydroxybenzenes. According to the above mechanism, the partition coefficients of dihydroxybenzenes in the surfactant solutions are calculated. The surface tension of the system was also measured to confirm the voltammetry results. The results obtained from surface tension measurement are well consistent with the voltammetry results.