The Korean National Health Insurance, which provides universal coverage for the entire Korean population, is now facing financial instability. Frequent emergency department (ED) users may represent a medically vulnerable population who could benefit from interventions that both improve care and lower costs. To understand the nature of frequent ED users in Korea, we analyzed claims data from a population-based national representative sample. We performed both bivariate and multivariable analyses to investigate the association between patient characteristics and frequent ED use (4+ ED visits in a year) using claims data of a 1% random sample of the Korean population, collected in 2009. Among 156,246 total ED users, 4,835 (3.1%) were frequent ED users. These patients accounted for 14% of 209,326 total ED visits and 17.2% of $76,253,784 total medical expenses generated from all ED visits in the 1% data sample. Frequent ED users tended to be older, male, and of lower socio-economic status compared with occasional ED users (p < 0.001 for each). Moreover, frequent ED users had longer stays in the hospital when admitted, higher probability of undergoing an operative procedure, and increased mortality. Among 8,425 primary diagnoses, alcohol-related complaints and schizophrenia showed the strongest positive correlation with the number of ED visits. Among the frequent ED users, mortality and annual outpatient department visits were significantly lower in the alcohol-related patient subgroup compared with other frequent ED users; furthermore, the rate was even lower than that for non-frequent ED users. Our findings suggest that expanding mental health and alcohol treatment programs may be a reasonable strategy to decrease the dependence of these patients on the ED.