As cities are extremely vulnerable to the impacts of climate change, they are fundamental in addressing these changes. However, streets, which are external spaces accessed by citizens in daily life, play an important role in improving the urban environment and public health. This study considered Busan in South Korea as a case study to investigate street canyons, including street canyon geometries and tree configurations, of old, present, and new city centers. The influence of morphological factors on the microclimate and outdoor thermal comfort was evaluated using the ENVI-met program for extremely hot weather. Changes in the street width, street orientation, and street canyon aspect ratio had a significantly higher impact on the microclimate and thermal comfort index (p < 0.01). These results indicated that the orientation of the main street should be consistent with the prevailing wind direction of Busan. Further, the shading of adjacent buildings improved the outdoor thermal comfort and reduced the significance of tree configuration in deeper street canyons. In addition, tree height had a more significant impact on street environment than other tree configuration factors, especially when the tree height increased from 9 m to 12 m. We recommended that the thermal comfort level can be improved by dynamically adjusting the relationship between the planting distance and tree height in streets having shallow street canyons.