As for the relationship between market structure and technological innovation, it is an old industrial organizational paradigm. But most of the theories were developed under the context of developed countries and concerned mostly in the relationship between market structure and innovation. Therefore this paper tries to analyze the relationship among market structure, technological innovation and industrial competitive advantage by analyzing the practice of the industrial development of developing countries and is going to offer a theory for the policy makers of late comers. In this paper, two paths for catching up countries are putted forward and simulations are conducted by a dynamic model.