Aqueous decanoic acid/sodium decanaote systems were studied as a function of pH and concentration, up to 0.3 M decanoic acid/sodium decanoate, by electron spin resonance (ESR) spectroscopy using three different amphiphilic spin labels. The distribution of the spin labels between vesicles and micelles as well as their dynamic properties were determined by quantitative analysis of the ESR spectra using two novel simulation software packages. Rotational correlation time of the labels in micelles was found to increase with decreasing pH, with substantial increase in the region where vesicles were formed (7.8<pH<8). In the interval 6.5<pH<7.8, the coexistence of vesicles and micelles was observed. Presence of vesicles was confirmed by the captured aqueous volume, determined independently with a hydrophilic spin label. The ESR measurements indicate that decanoic acid vesicle formation observed as the concentration is increased between 0.01 M and 0.03 M at pH 7.0 most likely occurs via the formation of micelles which remain in coexistence with the vesicles, even if the concentration is well above these values.