The micellization behavior of binary surfactant mixtures containing anionic surfactants with different counter ions viz. sodium dodecyl sulphate (NaDS)and magnesium dodecyl sulphate (Mg(DS)2) and nonionic surfactants with different head group structures viz. n-dodecyl-β-D-maltoside (DDM) and dodecyl tetraethylene glycol ether (Brij30) in aqueous solution were investigated respectively by surface tension and fluorescence probe methods. The results indicated that strong synergistic effect exist between the two components of micelles of all the mixed surfactant systems. The magnitude of synergistic effect followed the order Mg(DS)2/DDM＜NaDS/DDM＜Mg(DS)2/Brij30＜NaDS/Brij30. Mg(DS)2 had less interaction with nonionic surfactants in comparison to NaDS. Mg2+ leaded to MDS in mixed micelle was less far away from the standard state compare with Na+ 。The results of the interaction between surfactants and the contribution of free energy by Maeda’s model were consistent with that of Rubingh’s theory. Moreover, nonionic surfactant with the flexible head group encourages the formation of the mixed micelle and counter ions have little great impact on the aggregation and micropolarity of mixed surfactant systems.