A series of trimeric n-alkylphenol polyoxyethylene surfactants (TAP) were successfully synthesized and the molecular structure were confirmed by NMR, FTIR spectrum and elemental analysis. Using the same synthesis route, the trimeric nonylphenol polyoxyethylene surfactant (TNP) was synthesized using industrial product nonylphenol and paraformaldehyde, and its molecular structure was characterized by (HNMR)-H-1, FTIR spectrum and elemental analysis. The optimal reaction conditions were established. The surface activity properties of TAP and TNP (such as the critical micelle concentration (cmc), the values of surface tension at the cmc (gamma(cmc)), the maximum surface excess concentration (Gamma(cmc)), and the minimum surface area per surfactant molecule (A(cmc))), were determined by means of Wilhelmy plate method and steady-state fluorescence probe method, respectively. The experimental results show that the lengths of the hydrophilic group oxyethylene (EO) chains and hydrophobic group methylene chains have an influence on the cmc, gamma(cmc), Gamma(cmc), and A(cmc) of series of surfactants. Furthermore, TAP are arranged to staggered three-dimensional array mode at the air-water interface, which has exhibited better surface properties, such as low cmc values, strong adsorption affinities and wet abilities. (C) 2010 Elsevier B.V. All rights reserved.