It is crucial to consider structural design issues in Trombe wall (T-wall) buildings to promote more suitable indoor climates and thermal comfort standards. Therefore, the present study examined the impact of two different T-wall designs and six different roof types on the energy and operational efficiency of a building located in a low-temperature and high-humidity winter climate. Ansys-CFX 15.0 software was employed to simulate the thermal and fluid dynamics behavior of the T-wall system, and flow, thermal comfort, energy, and exergy analyses were conducted. Three-dimensional simulation results and the pertinent literature data showed a good level of agreement, and the accuracy of the model was ensured. Outcomes revealed an average air velocity variation of 0.186 m/s and maximum average indoor air temperature variation of 3.3 °C between the six roof geometries. The highest air speed (0.988 m/s) was recorded for the gambrel roof while the lowest one (0.802 m/s) was recorded for the typical flat roof. The shed roof right with a rounded T-wall was more comfortable for standing and sitting activity than the others for the two T-wall shapes, and, at Y = 0.6 m and Y = 1.1 m, the average predicted percentages of dissatisfied (PPD) values were 31 and 28%, respectively. Furthermore, it was determined in the study that solar radiation intensity and T-wall and roof geometries had a significant effect on energy and exergy efficiency, and high energy and exergy efficiencies were achieved at higher solar intensity values. The best energy and exergy efficiencies were obtained for the butterfly and shed roof configurations. This study can serve as a reference for the thermal environment design of buildings with T-walls.