The firms in cluster acquire information and assets through the business and political network tie to carry on the technological entrepreneurship. The paper focuses on the following three points to explain the influencing mechanism of cluster network tie on technological entrepreneurship: Whether and how the network tie in the cluster influences on technological entrepreneurship, and the adjusting role of the dysfunctional competition between them. Based on the empirical study of six clusters in Zhejiang province, the results reveal that: Firstly, firms’ business and political network ties have significantly positive effects on firms’ technological entrepreneurship with the former’s influence greater than the latter. Business network tie facilitates the acquisition of information resources, while the political network tie reinforces the acquisition of assets. Secondly, the relationship between business network tie and firms’ technological entrepreneurship is partly mediated by information resource acquisition; the relationship between political network tie and firms’ technological entrepreneurship is fully mediated by assets resource acquisition. Thirdly, dysfunctional competition plays a negative moderating role between business network tie in the cluster and firms’ technological entrepreneurship, but not a significant moderating role between political network tie in the cluster and firms’ technological entrepreneurship.