With the challenge of global climate change, the development of new energy industry plays an important role in the pursuit of green innovation and sustainable development. China′s photovoltaic industry started in the 1960s, although its development was slow in early stage. While China′s photovoltaic industry has developed rapidly in the past decade, and has successfully caught up with and surpassed other countries to become a global leader in photovoltaic industry. Based on the perspective of innovation ecosystem, this paper explores the mechanism of catching up and surpassing of China′s photovoltaic industry. Through the case study of Chinese photovoltaic industry, it is found that in the entry stage, the deployment policies of photovoltaic technologies in developed countries not only affect the local market, but also have spillover effects on developing countries, thus providing an international market demand window of opportunity for China′s photovoltaic industry. Chinese photovoltaic firms take advantage of this window of opportunity to improve their performance, by embedding in the global innovation ecosystem for technology introduction, establishment of legitimacy and access to capital in the international market. Moreover, the global photovoltaic industry develops slowly, since many advanced core technologies cannot be industrialized. In particular, the deployment policies urge firms to transform the core technology of photovoltaic into products and put them into the market in advance. Therefore, there are still many challenges in the complementary technologies of the global photovoltaic industry, which provids complementary technological windows of opportunity in innovation ecosystem for latecomers. In the catching up and surpassing stage, Chinese PV firms seize the complementary technological windows of opportunity in the innovation ecosystem, to build the local innovation ecosystem for improving their performance by selectively knowledge sharing, collaborating with the firms upstream and downstream for innovation, forming the whole industrial chain, and cluster effect and complementary technologies innovation, thus catch up and surpass the global leaders in other developed countries. In addition, in the surpassing stage, the demand of the international market not only provides opportunities for China′s photovoltaic industry, but also brings challenges due to the financial crisis, antidumping duties and countervailing duties, which decrease the international market demand rapidly. While the Chinese government helps domestic photovoltaic firms cultivate local downstream market demand, thus Chinese photovoltaic firms have stabilized the local innovation ecosystem by taking advantage of the institutional/policy windows of opportunity, and effectively coordinated the upstream and downstream partners to jointly innovate, maintaining the leading position in the global solar photovoltaic industry. This paper believes that the success of China′s photovoltaic industry to catch up with the leaders depends on the application of the innovation ecosystem strategy. Understanding the catching up of new energy industry in developing countries needs to be analyzed from the perspective of the innovation ecosystem. Especially at the technical level, the catching up of latecomers should not only pay attention to the core technological innovation, but also pay attention to the complementary technological innovation in the innovation ecosystem. Furthermore, firms in developing countries can make contributions to the new energy industry by improving complementary technologies, so as to significantly reduce prices and guide the industry into the growth stage.