Association between short-term exposure to fine particulate matter (PM2.5) and mortality or morbidity varies geographically, and this variation could be due to different chemical composition affected by local sources. However, there have been only a few Asian studies possibly due to limited monitoring data. Using nationwide regulatory monitoring data of PM2.5 chemical components in South Korea, we aimed to compare the associations between daily exposure to PM2.5 components and mortality across six major cities. We obtained daily 24-h concentrations of PM2.5 and 11 PM2.5 components measured from 2013 to 2015 at single sites located in residential areas. We used death certificate data to compute the daily counts of nonaccidental, cardiovascular, and respiratory deaths. Using the generalized additive model, we estimated relative risks of daily mortality for an interquartile range increase in each pollutant concentration, while controlling for a longer-term time trend and meteorology. While elemental carbon was consistently associated with nonaccidental mortality across all cities, nickel and vanadium were strongly associated with respiratory or cardiovascular mortality in Busan and Ulsan, two large port cities. Our study shows that PM2.5 components responsible for PM2.5-associated mortality differed across cities depending on the dominant pollution sources, such as traffic and oil combustion.