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Greece is characterized by a significant warming trend in recent decades, accompanied by increasing frequency, intensity, and duration of heat waves (HWs). A particularly devastating HW that affected the country was the late July/early August 2021 event (JA2021HW), which lasted for 9 days (July 28–August 5). Focusing on the hottest day of the event (August 3), the main characteristics of JA2021HW are presented in the current study, using model reanalysis data and up to 11‐year observations derived from the dense network of ground‐based weather stations operated by the Meteo Unit at the National Observatory of Athens (NOA). This analysis highlights the severity of JA2021HW, especially in the central and southernmost regions of Greece. Most importantly, the impact of the direct effect of anthropogenic greenhouse gases to the examined extreme event, in terms of intensity and probability of occurrence, is examined by employing a regional 31‐member ensemble (ENS) modeling approach based on Weather Research and Forecasting (WRF) model, which is operationally used by NOA/Meteo. Firstly, WRF is validated under 7‐day lead‐time ENS simulations with current‐state greenhouse gas (GHG) concentrations (GHG_2021 ENS), showing a robust model performance in replicating the JA2021HW's magnitude on August 3rd. Then, 7‐day lead‐time ENS simulations with the GHG concentrations reduced to the pre‐industrial (1854) levels (GHG_1854 ENS) are performed and compared to the GHG_2021 ENS experiment. The results reveal a contribution of the immediate anthropogenic warming due to the increased GHG concentrations to the JA2021HW intensity in West and South continental and insular Greece, which can be important in the framework of the human health impacts of extreme temperatures. For the event's occurrence probability, no robust evidence of any change could be derived. These statements are partially constrained by the fact that only the direct GHG effect on the timescale of a few days was examined. [ABSTRACT FROM AUTHOR]