Its rationality of temperature and water vapor partial pressure as driving potential for coupled heat and moisture transfer was demonstrated based on non-equilibrium thermodynamics. As water vapor partial pressure is a function of moisture content and temperature, mathematical model of coupled heat and moisture transfer for multilayer wall were established according to the theory of total differential. The approximate expressions between humidity content and relative humidity of air used in Budaiwi method could be avoided. The coefficients of mathematical model were simplified and could improve efficiency of solution. Its validation was illustrated by contrasting and analyzing the simulation results of a multilayer wall.