In an innovation driven business environment, cross-border access to resources is important for companies to improve innovation capabilities and development performance. Based on the previous research, it shows that there are barriers to cross domain communication among alliance firms because of the restriction of multidimensional ties and dyads. Simmelian ties, as a form of alliance network with ternary connections, it effectively restrained opportunism and self-interest in the cooperation process and take a crucial role to evaluate innovation related performance in corporation. Based on the theory of Simmelian, this paper builds a theoretical framework and proposes corresponding research hypotheses between Simmelian ties and enterprise innovation performance. After designing questionnaires, collecting data and conducting empirical analysis to test theoretical models and hypotheses. Results have shown that: (1) Simmelian ties generally have a positive impact on enterprise innovation performance. (2) Knowledge capturing and knowledge integration play a partial intermediary role between Simmelian ties and enterprise innovation performance, and the mediating chain formed by the two variables plays a serial mediating role in the effect. (3) Network routines significantly positively moderates the relationship between Simmelian ties and knowledge capturing. And also, the positive relationship between Simmelian ties and enterprise innovation performance is also actively moderated by network routines. The conclusion of this study is meaningful for companies to establish of Simmelian ties, improve knowledge management capabilities and further promote enterprise innovation performance.