To predict the surface tension of binary liquid systems, an empirical model is proposed using the partial least squares (PLS) based on the multivariate statistical analysis method. Required parameters for the PLS method to predict the surface tension of binary systems are composed of the thermophysical properties of only pure substances such as critical temperature, critical pressure, critical volume, molar volume, viscosity and vapor pressure for input data block (X) and the reported experimental surface tension data for output data block (Y). The data set for the experimental surface tension of binary liquid systems is divided into the training set for regression and the test set for predicting. An average relative error (%) results of regression and prediction indicate that the PLS method can be a useful tool for predicting the surface tension of liquid binary systems.