Cesium perfluorooctanoate molecules are investigated by NMR spectroscopy in the lamellar phase of their aqueous solution. The particular NMR method, ¹³C-detected, ¹⁹F-decoupled separated-local-field (SLF) spectroscopy, provides the dipolar splitting of each ¹³C spin to its ¹⁹F neighbors. These dipolar splittings are interpreted in terms of the molecular C-F bond order parameters of each difluoromethylene and trifluoromethyl group. The obtained variation of this order parameter along the fluoroalkyl chain strengthens the conclusion from an earlier, model-dependent study (Furo, I.; Sitnikov, R. Langmuir 1999, 15, 2669): perfluorinated surfactant chains are significantly more rigid than their hydrogenated counterparts.