The two-pulse and three-pulse electron spin echo techniques were applied to investigate the behavior of doxyl stearic acid spin probes in micellar aqueous solutions of ammonium perfluorooctanoate. Three doxyl stearic acids with the nitroxide group in different positions on the alkyl chain were used as spin probes, and deuteriated water was used to study the deuterium modulation of the echo signals. The experimental patterns were interpreted by best-fit spectra calculated by taking into account both the echo decay and the nuclear modulation. The analysis determines the number of deuterium nuclei in the surroundings of the NO groups and the time constant for the electron spin reorientation causing spectral diffusion and echo decay. From these data we conclude that water molecules belonging to the NO solvation sphere were maintained in the micelles and that the long-chain nitroxide probes, were tilted in the micelle core in order to occupy regions with relatively easy water accessibility which was slightly higher for 12-DXSA than for 5- and 16-DXSA. The modulation of the hyperfine couplings of the methyl protons due to their rotational motion was the main mechanism contributing to the echo decay.