The equilibrium and dynamic surface properties of anionic surfactant alcohol ether sulfate with different EO distribution(C-AE2S and N-AE2S) and cationic surfactant tetradecyltrimethylammonium bromide (TTAB) mixtures under different molar ratios were investigated. Their surface activities, adsorption, and spreading performances were investigated by static/dynamic surface tension measurements, molecular dynamics simulation, and dynamic contact angle techniques at 298 K. The static surface tension analysis reveals that the critical micellization concentration (cmc) values and the surface tension at cmc (γ cmc) of the binary systems are much lower than that of the individual component. Compared with C-AE2S/TTAB, N-AE2S/TTAB systems have higher cmc and lower γ cmc. It was found from the molecular dynamics simulation that negative charges of C-AE2S were drastically neutralized by the positively-charged TTAB at the interface in the system of C-AE2S/TTAB. The dynamic surface tension results indicate that the adsorption process of aqueous solutions for both C-AE2S/TTAB and N-AE2S/TTAB are mixed diffusion-kinetic adsorption mechanisms. From the dynamic contact angle measurements, it could be obtained that the mixtures exhibit better spreading behavior than that of the individual component and N-AE2S/TTAB systems have lower contact angles than that of C-AE2S/TTAB at the same mixing ratios.