Abstract: It is very important to enhance the breakthrough innovation performance by using the alliance portfolio management capabilities to acquire and utilize the external key resources of the enterprise. Based on the resource-based view, a theoretical model of alliance portfolio management ability, key resource acquisition, and breakthrough innovation performance is constructed. By means of questionnaire surveys and statistical analysis, we conclude that all the three dimensions of alliance portfolio management capabilities have significant positive impacts on breakthrough innovation performance. Relational governance as well as portfolio coordination affects the acquisition of key resources significantly, which then obviously affects the breakthrough innovation performance. The acquisition of key resources plays full mediating role between relational governance and breakthrough innovation performance, and part mediating role between portfolio coordination and breakthrough innovation performance.