Accurately locating key nodes and corridors of an urban heat island (UHI) is the basis for effectively mitigating a regional surface UHI. However, we still lack appropriate methods to describe it, especially considering the interaction between UHIs and the role of connectivity (network). Specifically, previous studies paid much attention to the raster and vector perspective—based on standard landscape configuration metrics that only provide an overall statistic over the entire study area without further indicating locations where different types of pattern and fragmentation occur. Therefore, by reverse thinking, here we attempt to propose a new method from the graph perspective which integrates morphological spatial pattern analysis (MSPA)—which is used to characterize binary patterns with emphasis on connections between their parts as measured at varying analysis scales, and habitat availability indices to evaluate and mitigate regional surface UHI. We selected the Pearl River Delta Metropolitan Region (PRDR), one of the most rapidly urbanized regions in the world as the case study (1995–2015). The results of the case study showed: (1) the core (UHI) type accounts for the vast majority of the MSPA model, with the relative land surface temperature (LST) rises, the proportion of the core type will increase, and it could influence the edge (UHI) type significantly; (2) the branch, bridge, and islet (UHI) types have similar results to the lower temperature (4 < Relative LST ≤ 6) area and account for the majority, indicating that these types are more susceptible to their surrounding environment; (3) the importance and extreme importance area (node) from 1995 to 2015 have increased significantly and mainly distributed in the urbanized areas, which means cooling measures need to be implemented in these areas in order of priority. Shifting the research logic of UHI evaluation and mitigation from “patch” to “network”, we hold the point that the method (reverse thinking) has significant theoretical and practical implications for mitigating regional UHI and urban climate-resilience.