Urban heat islands (UHIs) constitute an important ecological problem in cities. Ecological space has a positive effect on UHI mitigation, which can be effectively organized in the form of ecological networks. In this study, the framework for structural UHI improvement based on ecological networks considering the source-corridor model is proposed to examine the spatial threshold of the thermal effect of ecological network factors. Additionally, the cooling mechanism of each constituent element in the ecological network context is further explored. The results demonstrate that (1) an obvious cold and heat island spatial aggregation distribution exists in the Xuzhou main urban area, and land of the same land use type exhibits the dual thermal environmental properties of cold and heat islands through its spatial distribution and characteristics. Ecological space is the main bearing area of cold islands. (2) The ecological network in the main urban area of Xuzhou city occurs at a moderately complex level, and the overall network efficiency is acceptable; the network connectivity is low, while the network loop distribution is uneven. (3) Ecological networks represent an effective spatial means to improve overall UHI patterns. The ecological source area cooling threshold is 300 m, and the optimal threshold is 100 m, while the ecological corridor width threshold is 500 m and 60 m, respectively. (4) Within the optimal threshold in the context of ecological networks, the temperature of ecological sources in category G land is influenced by NDBI and FVC; ecological corridors are mainly influenced by NDBI. The results can provide a quantitative basis for urban ecological network planning considering UHI improvement and a reference for urban thermal environment research within different ecological substrates and planning and control systems in other countries and regions worldwide.