Vulnerability to heat was examined for populations of 6 major cities in South Korea (Seoul, Incheon, Daejeon, Gwangju, Daegu, and Busan). Daily excess mortality and maximum temperature from 1991 to 2005 were employed in this study. The results show that the standardized mortality increase associated with a $1^{circ}C$ increase in daily maximum temperature above the city-specific threshold explains the heat acclimatization effect better than the threshold temperature itself. The estimated increase in mortality (standardized per 10 million population) associated with a $1^{circ}C$ increase in temperature above the threshold is 4.8 in Incheon, 4.7 in Seoul, 4.3 in Daejeon, 2.8 in Gwangju, 2.4 in Daegu, and 1.5 in Busan, well reflecting the latitudinal locations and local climates of each city. Climate models project more frequent, more intense, and longer lasting heat waves in most land areas in both hemispheres in the 21st century under increasing greenhouse gas concentrations. In order to mitigate the adverse human health impacts due to excess heat, more detailed characteristics of acclimatization to heat need to be understood and quantified.