The stability and interactions in thin wetting films between the silica surface and air bubble containing (a) straight chain C10 amine and (b) cationic/anionic surfactant mixture of a straight chain C10 amine with sodium C8, C10 and (straight chain) C12 sulfonates, were studied using the microscopic thin wetting film method developed by Platikanov [D. Platikanov, J. Phys. Chem. 68 (1964) 3619]. Film lifetimes, three-phase contact (TPC) expansion rate, receding contact angles and surface tension were measured. The presence of the mixed cationic/anionic surfactants was found to lessen contact angles and suppresses the thin aqueous film rupture, thus inducing longer film lifetime, as compared to the pure amine system. In the case of mixed surfactants heterocoagulation could arise through the formation of positively charged interfacial complexes. Mixed solution of cationic and anionic surfactants shows synergistic lowering in surface tension. The formation of the interfacial complex at the air/solution interface was confirmed by surface tension data. It was also shown, that the chain length compatibility between the anionic and cationic surfactants system controls the strength of the interfacial complex. The observed phenomena were discussed in terms of the electrostatic heterocoagulation theory, where the interactions can be attractive or repulsive depending on the different surface activity and charge of the respective surfactants at the two interfaces.