Purpose Heat gain in buildings occurs due to heat transfer through the building fabric or envelope, especially the walls and roof. The purpose of this paper is to identify and recommend the suitable wall materials for better thermal performance in buildings in warm and hot climatic zones of India. As India lies between the tropic of cancer and the equator, the solar radiation from the sun falls more on the walls than the roofs of the buildings. Thus, it is imperative to protect the walls from heat gain to promote thermal comfort in naturally ventilated buildings and reduce the energy loads due to artificial cooling systems in air-conditioned buildings. Design/methodology/approach In this paper, an investigation of heat flow characteristics in steady-state and the transient state for five different uninsulated wall structures using computational fluid dynamics (CFD) software has been carried out. The climate conditions at Madurai, India have been considered for this study. Findings The findings of the study revealed that aerated autoclaved concrete (AAC) and hollow clay blocks (HCB) for external walls in naturally ventilated buildings in warm climatic regions could improve the building’s thermal performance index and reduce peak indoor operative temperature by about 6°C–7°C. The results of steady-state and transient state analysis were found to be in good agreement with the results of the reviewed literature. Research limitations/implications Over the past few decades, only very few architects and builders have been successful in influencing their clients to accept alternate materials such as AAC blocks, HCB, stabilized earth blocks, adobe blocks, fly-ash bricks as an alternate to conventional bricks in an attempt of highlighting their benefits, such as; materials that are easily available, more energy-efficient, can withstand the extreme weather conditions, promote thermal comfort and cost-effective. This paper provides strong evidence that AAC and HCB blocks are the most appropriate materials for improving the thermal performance of envelope walls in regions where the outdoor temperatures are above 40°C. Originality/value This paper has made an attempt to identify the appropriate wall materials for effective thermal performance in warm and hot climates. A comparative analysis between five different wall types under the existing solar conditions has been analyzed using CFD simulation study in steady-state and transient conditions under summer conditions and the appropriate wall materials have been suggested. There has been no attempt carried out so far to analyze the thermal performance of different walls using 24 h transient approach in CFD.