Urban areas are often warmer than rural areas due to the phenomenon known as the “urban heat island” (UHI) effect, which can cause discomfort for those engaging in outdoor activities and can have a disproportionate impact on low-income communities, people of color, and the elderly. The intensity of the UHI effect is influenced by a variety of factors, including urban morphology, which can vary from one area to another. To investigate the relationship between outdoor thermal comfort and urban morphology in different urban blocks with varying social vulnerability status, this study developed a geographic information system (GIS)-based workflow that combined the “local climate zone” (LCZ) classification system and an urban microclimate assessment tool called ENVI-met. To demonstrate the effectiveness of this methodology, the study selected two different urban blocks in Philadelphia, Pennsylvania–with high and low social vulnerability indices (SVI)–to compare their microclimate conditions in association with urban morphological characteristics such as green coverage area, sky view factor (SVF), albedo, and street height to width (H/W) ratio. The results of the study showed that there was a strong correlation between tree and grass coverage and outdoor air and mean radiant temperature during hot seasons and extremely hot days, which in turn affected simulated predicted mean vote (PMV). The effects of greenery were more significant in the block associated with a low SVI, where nearly 50% of the site was covered by trees and grass, compared to only 0.02% of the other block associated with a high SVI. Furthermore, the investigation discovered that reduced SVF, along with increased albedo and H/W ratio, had a beneficial impact on the microclimate at the pedestrian level within the two studied urban blocks. This study provided an effective and easy-to-implement method for tackling the inequity issue of outdoor thermal comfort and urban morphology at fine geographic scales.