The human-biometeorological conditions in Ukraine during two mega-heat waves were analyzed. The evaluation is based on physiologically equivalent temperature (PET). The calculation of PET is performed utilizing the RayMan model. The results revealed these two mega-heat waves produced strenuous human-biometeorological conditions on the territory of Ukraine. During the summer 2010 mega-heat wave, strong and extreme heat stress prevailed at about midday at the stations where this atmospheric phenomenon was observed. The mega-heat wave of August 2015 was characterized by a lower heat load. The diurnal variation of PET values during the researched mega-HW was similar to that of the diurnal variation of air temperature with minimum values in the early morning and maximum values in the afternoon. On the territory where mega-heat waves were observed, the number of days during which heat stress occurred for 9 h amounted to 97.6% for the period from 31 July to 12 August 2010 and 77.1% for the mega-heat wave of August 2015.