Due to the Productivity shocks, there exist inherently systemic biases when using purchasing power parity as the equilibrium real exchange rate measure standard. In this paper, based on characteristic of Chinese economic transformation, considering demographic and weakened Balassa-Samuelson effect, we re-estimate the equilibrium level of real exchange rate of RMB with the quarterly frequency data since 1994, and measuring the misalignment of RMB real exchange rate. The empirical results show that the behavioral equilibrium exchange rate model is a reasonable analytical framework of RMB equilibrium real exchange rate, and in the sample period, the real exchange rate of RMB is robust, demographic is an important variable affecting the RMB equilibrium exchange rate. The real exchange rate of RMB is closely related to China's economic development strategy.