A sound ecological security network (ESN) promotes the interconnection of ecological sources, improves the pattern of ecological security, and alleviates the degradation of an ecosystem. Rapid urbanization and land use changes may lead to serious fragmentation and islanding of landscape patches and further to deep disturbance of regional ESNs. However, most studies in the recent years focused on the methodological development of ESN identification, reconstruction, and optimization, but lacked the systematic assessment of the network after its construction. The purpose of this study is to use complex network analysis to systematically assess the constructed ESN for the urban agglomeration around Hangzhou (UAHB), a rapid urbanization region in China. By integrating landscape ecology theory, graph theory, and complex network analysis, we abstracted the ESN into a topological network and developed an index system to assess the abstracted network, which was based on the structural elements of the topological network (nodes, edges, and the overall network). Our results show that the connectivity and stability of the UAHB’s ESN have been improved in the last 20 years, although isolated nodes are still existing in the ESN. Our study also shows that the network’s robustness under human disturbance has been affected more than that under non-human disturbance. Finally, we proposed five optimization strategies from the perspective of topological structure and ecological function to maintain a sustainable and well-protected ecological system.