In this paper, we use the Multi-state Markov model to explore the impact of trade openness and terms of trade volatility on exchange rate regime transition through sample data from 93 countries between 1970 and 2010. In addition, we show the probability of exchange rate regime transition path. The empirical result shows that under the control of macro-politics and other economic conditions, the openness of trade and the terms of trade volatility have no significant effect on the transition of the exchange rate regime, that is, a higher degree of trade openness has not prompted the economy exit from a status to a fixed regime, and the terms of trade volatility did not turn the economy into a floating exchange rate system. And in the long run, we find the economy prefers an intermediate exchange rate regime not the "intermediate system disappearing theory".