Urban compact buildings impose large frictional drag on boundary-layer air flow and create stagnant air within the building environment. It results in exacerbating the street-level outdoor thermal comfort (OTC). It is common to perform in-situ measurements of the OTC in different urban forms and to study their relationship. However, it is impossible to do so from a planning perspective because of the absence of physical planned urban forms. Our objective was to quantify the thermal environment and OTC in different planned complex urban forms by well-validated numerical models. We coupled a computational fluid dynamics (CFD) model to an OTC (Rayman) model to study the OTC. The κ–ω SST turbulent model was adopted for the CFD simulations, with accuracy of the turbulent model validated by wind tunnel measurements. The highest calculated air temperature within the street canyon of a planned bulky urban form could reach more than 5 °C higher than the surrounding environment. Within the tested urban forms, our coupled model predicted mean radiant temperature comparable with measurements in the literature. The model also produced sensible street-level physiologically equivalent temperatures (PETs) when comparing with those listed in the human thermal sensation categories. In the morning, the predicted PETs within all the urban forms were lower than that in open areas, which indicated that the shading of buildings effectively reduced the PET increase due to solar irradiance. At noon, increases in PETs by more than 10 °C relative to the morning situation indicated that when the buildings acted as heat sources after insolation absorption, increase in the air temperature at the street intersection and in the street canyon made an important contribution to the receiver PETs. The reduction in building lengths and increase in the low-level porosity were the most effective ways to reduce the heat stress at the pedestrian-level.