Due to the coupling impacts of solar radiation, wind, air temperature and other environmental parameters, the temperature field of steel structures is significantly non-uniform during their construction and service stages. Corrugated web steel beams have gained popularity in structural engineering during the last few decades, while their thermal actions are barely investigated. In this paper, both experimental and numerical investigations were conducted to reveal the non-uniform features and time variation of the corrugated web steel beams under various environmental conditions. The heat-transfer simulation model was established and verified using the experimental temperature data. Both the experiment and simulation results demonstrate that the steel beam has a complicated and non-uniform temperature field. Moreover, 2-year continuous numerical simulations of steel beams’ thermal actions regarding eight different cities were carried out to investigate the long-term temperature variations. Finally, based on the long-term simulation results and extreme value analysis (EVA), the representative values of steel beams’ daily temperature difference with a 50-year return period were determined. The extreme temperature difference of the steel beam in Harbin reached up to 46.9 °C, while the extreme temperature difference in Haikou was 28.8 °C. The extreme temperature difference is highly associated with the steel beam’s location and surrounding climate. Ideally, the outcomes will provide some contributions for the structural design regarding the corrugated web steel beam.