The surfactant properties of solutes play an important role in the sonochemistry and sonoluminescence of aqueous solutions. Recently, it has been shown, for relatively low molecular weight surfactants, that these effects can be correlated with the Gibbs surface excess of the solute. In the present study we investigate whether this correlation is valid for relatively high molecular weight surfactants and the mechanisms of surfactant decomposition during sonolysis. Sonolysis of argon-saturated aqueous solutions of nonvolatile surfactants [n-alkanesulfonates, n-alkyl sulfates, n-alkylammoniopropanesulfonates (APS), and poly(oxyethylenes) (POE)] was investigated by EPR and spin-trapping with 3,5-dibromo-4-nitrosobenzenesulfonate. Secondary carbon radicals (-.CH-), formed by abstraction reactions, were observed for all surfactants that were sonicated. The yield of primary carbon (-.CH(2)) and methyl (.CH(3)) radicals that are formed by pyrolysis is greatest for the zwitterionic (i.e., APS) and nonionic surfactants (i.e., POE). The yield of (-.CH-) radicals was measured following sonolysis of n-alkyl anionic surfactants [sodium pentanesulfonate (SPSo), sodium octanesulfonate (SOSo), sodium octyl sulfate (SOS), and sodium dodecyl sulfate (SDS)]. In the concentration range of 0-0.3 mM, the -.CH- radical yield increases in the order SDS approximately equal to SOS approximately equal to SOSo > SPSo. At higher concentrations, a plateau in the maximum (-.CH-) radical yield is reached for each surfactant, which follows the order SPSo > SOS approximately equal to SOSo > SDS; i.e., the radical scavenging efficiency increases with decreasing n-alkyl chain length. A similar trend was observed for the .CH(3) yield following sonolysis of a homologous series of n-alkyl APS surfactants. The results show that the Gibbs surface excess of certain nonvolatile surfactants does not correlate with the extent of decomposition following sonolysis in aqueous solutions. Instead, the decomposition of surfactants depends on their chemical structure and their ability to equilibrate between the bulk solution and the gas/solution interface of cavitation bubbles.