The effects of heat treatment on membrane fouling resistance and the rejection of small and neutral solutes by reverse osmosis (RO) membranes were elucidated. RO membrane modification by heat treatment reduced fouling and improved boron rejection. However, heat treatment also caused a decrease in the water permeability of RO membranes. Significant improvement on fouling resistance by heat treatment was observed when RO concentrate was used to simulate a feed solution with high fouling propensity. The improved fouling resistance is likely to be due to changes in the hydrophobic interaction between the membrane surface and foulants. Boron rejection by the ESPA2 membrane was enhanced by heat treatment from 26 to 68% (when evaluated at the permeate flux of 20 L/m2 h). Positron annihilation lifetime spectroscopy revealed that heat treatment did not significantly influence the free-volume hole-radius of the membrane active skin layer. The results reported in this study suggested that changes in the other membrane properties such as free-volume fraction and thickness may be the main cause improving boron rejection.