Micellization and adsorption at the air-solution interface of binary mixtures of the triblock copolymer of ethylene oxide and propylene oxide, EO23PO52EO23 (EPE), and the surfactants sodium dodecyl sulfate (SDS), dodecyl trimethylammonium chloride (DTAC), and tetraethylene glycol monooctyl ether (C8EO4) have been studied by neutron reflectivity and surface tension. The synergistic attractive interaction between the polymer and the ionic surfactants has been analyzed in the framework of the pseudo phase approximation and gives rise to a stronger interaction for EPE/SDS than EPE/DTAC. In contrast, the interaction of the nonionic surfactant C8EO4 with the copolymer EPE shows an unexpected and rather different behavior, resulting in a strongly repulsive interaction, characterized by a positive interaction parameter. The neutron reflectivity measurements of the surface excess, where the predicted and measured surface excesses are directly compared, provide evidence that challenges the applicability of the pseudo phase approximation for describing the surface mixing behavior. Structural information on the mixed adsorbed layer provides evidence which in part explains the observed discrepancies between the measured surface excesses and the behavior predicted from the pseudo phase approximation. Furthermore the structural evidence can be use to rationalize the differences in behavior observed between the ionic and nonionic surfactants.