Knowledge flow, reflecting knowledge dynamics, was measured through talent exchange, intangible asset and R&D alliance. To analyze the influence of knowledge flow on the technological competence, data were collected from 262 enterprises, the mediating of exploratory and exploitative learning have been introduced, and the conceptual model has been built. The mediating effect and the hypotheses have been tested by using hierarchical regression and structural equation modeling. The results show that the role of “R&D alliance” in enhancing technological competence was more than “talent exchange”, while the effect of “intangible asset” was not significant. In addition, exploratory and exploitative learning played a part mediating role, and the indirect effect of “R&D alliance” and “talent exchange” under the mediating role of exploratory learning was greater than the direct effect. Hence, this study is helpful for firms to select knowledge flow, pay attention to “R&D alliance” and “talent exchange”, while purchase patent and technology cautiously, and maintain the constancy of exploitative learning to enhance the technological competence in practice.