This study conducted field measurements to explore the effects of street spatial structure on micrometeorological condition and air quality on both hot and cool days in Taipei City. Six street canyons with an aspect ratio of one, but varied in street orientation, street width, sky view factor, and number of planting strips, were selected for observations. In this case study, it was observed that, as well as the meso-scale phenomena, the local and micro-scale (street canyon structure) had influences on street air temperature, mean radiant temperature, and wind velocity. However, the local and micro-scales only had minor effects on relative humidity for both hot and cool days. Shade effect on temperature by street trees was observed; this effect could cause 2 degrees drop on mean radiant temperature and about 0.5 degree drop on air temperature. Our analyses and field measurements also revealed that, in some cases, concentrations of PM2.5 and PM10 were found to be correlated with local street canopy structure; however, in some cases, the meso-scale process was found to be the dominant factor. We also found that concentrations of CO and O3 were inversely correlated in the street canyon. The findings of this study provide introductory scientific data and guidelines for urban street designers to improve thermal comfort and air quality.