Episodes of hot weather and poor air quality pose significant consequences for public health. In this study, these episodes are addressed by applying the observational data of daily air temperature and ozone concentrations in an event-based risk assessment approach in order to detect individual heat and ozone events, as well as events of their co-occurrence in Berlin, Germany, in the years 2000 to 2014. Various threshold values are explored so as to identify these events and to search for the appropriate regressions between the threshold exceedances and mortality rates. The events are further analyzed in terms of their event-specific mortality rates and their temporal occurrences. The results reveal that at least 40% of all heat events during the study period are accompanied by increased ozone concentrations in Berlin, particularly the most intense and longest heat events. While ozone events alone are only weakly associated with increased mortality rates, elevated ozone concentrations during heat events are found to amplify mortality rates. We conclude that elevated air temperatures during heat events are one major driver for increased mortality rates in Berlin, but simultaneously occurring elevated ozone concentrations act as an additional stressor, leading to an increased risk for the regional population.