To investigate the structure?function relationship of novel extended surfactants and the mechanisms of reducing interfacial tensions (IFTs) at oil?water interface, the interfacial tension values of 13?P series 13?P（I?C₁₃（PO） _x S,x=5,10,15,20）with different concentrations of NaCl and n?hexane to n?tetradecane at fixed concentration were measured by rotary drop interfacial tension meter. The result indicates that at higher numbers of PO（x=15,20), the n_min values become higher with increasing concentration of NaCl. At lower numbers of PO（x=5,10), the n_min values become lower with increasing concentration of NaCl. It reflects two mechanisms on reducing IFTs: Hydrophilic lipophilic equilibrium effect and hydrophilic hydrophobic group in size matching effect, both of which work together, and the size matching plays a crucial role at lower numbers of PO and HLB dominates at higher numbers of PO.