Different structural patterns of waterfront green space networks in built-up areas have different synergistic cooling characteristics in cities. This study’s aim is to determine what kinds of spatial structures and morphologies of waterfront green spaces offer a good cooling effect, combined with three different typical patterns in Shanghai. A multidimensional spatial influence variable system based on the cooling effect was constructed to describe the spatial structural and morphological factors of the green space network. The ENVI-met 4.3 software, developed by Michael Bruse at Bochum, German, was used to simulate the microclimate distribution data, combined with the boosted regression tree (BRT) model and the correlation analysis method. The results showed that at the network level, the distance from the water body and the connectivity of green space had a stronger cooling correlation. The orientation of green corridors consistent with a summer monsoon had larger cooling effect ranges. In terms of spatial morphology, the vegetation sky view factor (SVF) and Vegetation Surface Albedo (VSAlbedo) had an important correlation with air temperature (T), and the green corridor with a 20–25 m width had the largest marginal effect on cooling. These results will provide useful guidance for urban climate adaptive planning and design.