A heat pipe heat exchanger (HPHE) was used to investigate the heat transfer performance of steam-air mixture condensation, analogous to the dew condensation of flue gas, when the steam volume fraction ranged from 0 to 20%, and the inlet temperature of steam-air mixture varied from 70 to 120 degrees C. Self-assembled monolayers (SAMs) treatment with n-octadecyl mercaptan was adopted to modify the condensation surface of the heat pipe. The comparisons were conducted to examine the influence of SAMs on condensation heat transfer of steam-air mixture vapor. The results indicate that the convection condensation heat transfer coefficient increases with the increase of steam volume fraction and Re number of the steam-air mixture. As the inlet temperature increases, the heat transfer coefficient decreases accordingly. The heat transfer performance can be improved by the SAMs surface, with a heat transfer enhancement ratio up to 1.6 at a condition of 20% of the steam volume fraction and 1500 Re number.