Sustainability and its component resilience have become an important issue that cannot be neglected in airspace planning and development. Resilience, as an emerging system concept, is critical to sustainability in many fields. With the rapidly growing demand in China’s air transportation sector, airspace congestion and flight delays have become a major issue in the fast development of this sector, and threatens the sustainability and resilience of air traffic control (ATC) systems such as waste of resources, air pollution, etc. Sectors, the basic units of an ATC system, play a significant role in ensuring the safe and smooth operations of day-to-day flights. In this paper, we apply the complex network theory to establish a model of China’s air sector network (CASN) and examine a series of characteristic parameters with an empirical analysis on its vulnerability and resilience. Through a simulation-based approach, the CASN’s resilience was quantitatively assessed with a resilience indicator (RI) in different scenarios to identify the optimal recovery strategy for building higher system resilience. The results show that the CASN has a lengthy average shortest path and a small clustering coefficient, which demonstrates a hybrid topological feature. We have also found that betweenness has the greatest impact on the resilience and has managerial implications to understand the relationship between vulnerability and resilience in CASN, so as to achieve the resilience and sustainability of CASN.