Abstract: This paper adopts the method of embedded case combining quantitative measurements. And it choose a leading enterprise-Dongfang Turbine Co., Ltd., which possesses technical innovation and excellent performance in the high-tech manufacturing in China, and studies the formation mechanism of internal and external collaborative innovation network in technical innovation under the function of knowledge environment in national innovation systems. The result shows that: the formation of internal and external collaborative innovation network is influenced by national innovation systems’ factors. Under the conditions of national education system undeveloped, labor market inadequate supply and intellectual property system imperfect, transaction cost in external collaboration is high relatively, enterprise is difficult to establish more external links, and collaborative innovation network appears a closed state. However, when the above conditions are improved, the result is opposite. More external links appeared, more open state developed. In this process, government’s role is mainly involving in guiding or financing the activities of technical innovation, providing preferential and supportive policy for excellent enterprises, and helping enterprises the collaborative innovation network formation and performance increasing.