Recent experimental studies have shown a preferential interaction of poly(vinylpyrrolidone) (PVP) toward the alkyl sulfate surfactants rather than toward those belonging to the alkyl sulfonate series. To gain information on the complex formation between PVP and the alkyl sulfate surfactants, we have performed H-1 and C-13 NMR and NOESY measurements on aqueous solutions of sodium decyl sulfate (C10OS) in the presence and absence of PVP at 1wt %. The results show that C10OS interacts with PVP, forming micelle-like clusters bound onto the polymer, and furthermore suggest that the PVP-C10OS complex formation implies the synergic effects of the electrostatic attractions between the surfactant headgroup and the nitrogen and oxygen atoms in the pyrrolidone ring of PVP and of the hydrophobic interaction between the surfactant alkyl moiety and the ring carbons of PVP.