The modelling of thermal exposure in outdoor urban environments is a highly topical challenge in modern climate research. This paper presents the results derived from a new micrometeorological model that employs an integrated biometeorology module to model Universal Thermal Climate Index (UTCI). This is PALM-4U, which includes an integrated human body-shape parameterization, deployed herein for a pilot domain in Prague, Czech Republic. The results highlight the key role of radiation in the spatiotemporal variability of thermal exposure in moderate-climate urban areas during summer days in terms of the way in which this directly affects thermal comfort through radiant temperature and indirectly through the complexity of turbulence in street canyons. The model simulations suggest that the highest thermal exposure may be expected within street canyons near the irradiated north sides of east–west streets and near streets oriented north–south. Heat exposure in streets increases in proximity to buildings with reflective paints. The lowest heat exposure during the day may be anticipated in tree-shaded courtyards. The cooling effect of trees may range from 4 °C to 9 °C in UTCI, and the cooling effect of grass in comparison with artificial paved surfaces in open public places may be from 2 °C to 5 °C UTCI. In general terms, this study illustrates that the PALM modelling system provides a new perspective on the spatiotemporal differentiation of thermal exposure at the pedestrian level; it may therefore contribute to more climate-sensitive urban planning.