Dodecyldimethylamine N-oxide (DDAO) is a zwitterionic surfactant with acid-base properties. The proton dissociation constant of this surfactant was determined by a novel potentiometric method at "controlled chemical potential" of the proton using a classical pH-glass electrode. When the DDAO was in its monomeric form, the pK(a) was about 5, consistent with the value commonly reported in the literature. However, a unique proton dissociation constant specific to the micellar form of this surfactant could not be obtained. We found that the acid-base behavior of the DDAO micelles depended on their environment. Indeed, we were able to establish thermodynamic relations linking the critical micellar concentration to the degree of protonation of the micelles. The experimental values were in good accordance with this model.