Dielectric relaxation behavior was investigated in the high-frequency range from 1 MHz to 20 GHz, or 6.3 x 10(6) to 1.3 x 10(11) rad s(-1) in angular frequency (omega), for aqueous Solutions of polyelectrolytes, random copolymers of styrene and sodium styrenesulfonate with it controlled degree Of sulfonation (X-S), by varying the concentration (c(P)) of polyelectrolytes at 25 degrees C. Besides dielectric measurements, the degree of Na+ binding (F-bin) to benzenesulfonate (BS-) groups for the polyelectrolytes in aqueous solution was determined as a function of X-S. Pronounced dielectric relaxation processes, which had no established assignments, were observed for omega > 10(9) rad s(-1). A dielectric relaxation mode found at a relaxation time of 0.12 its irrespective of c(P), with relaxation strength proportional to the product c(P)X(S), was attributed to the detachment of two to three hydrated water Molecules from BS- groups. Another relaxation in 0.9 ns, with relaxation strength proportional to c(P)X(S)F(bin), wits assigned to the rotation of BS--Na+ ion pairs with large dipole moments.