The interaction between poly(diallyldimethylammonium chloride) (PDADMAC) and ionic surfactant sodium decyl sulfate (C(10)SO(4)Na) in aqueous solution was investigated by means of dielectric relaxation spectroscopy. To better understand the interaction, the dielectric behaviors of PDADMAC solution and C(10)SO(4)Na solution were also separately studied. For PDADMAC solution, two relaxations were observed, which were attributed to the polarization of loosely bound counterions along the directions parallel and perpendicular to the PDADMAC chain. For C(10)SO(4)Na solution, dielectric relaxation was observed at submicellar concentrations, which is ascribed to the counterion diffusion around premicelles. For the aqueous solutions of a PDADMAC/C(10)SO(4)Na mixture with different C(10)SO(4)Na concentrations, three surfactant concentration regions characterized by different dielectric behaviors were observed. The dielectric behavior in different regions was discussed through comparing it with that of PDADMAC solution and C(10)SO(4)Na solution. The possible interaction pattern and microstructure of the PDADMAC/C(10)SO(4)Na complex were proposed on the basis of the dielectric behavior.