Summary Groundwater is nearly the sole source for freshwater supply on Jeju volcanic island because there are no perennial streams and rivers. Rain harvesting and subsequent artificial recharging have been conducted to meet growing freshwater demand in the island. We performed sequential samplings of harvested rainwater prior to the artificial injection in summer of 2008 at an artificial recharge site of western Jeju. Field measurements and chemical analyses of 313 rainwater samples revealed that there was a variation in chemical composition but the Na + K + SO 4 + Cl type was dominant. Predominance of Na and Cl was likely to be from sea salts while substantial amount of SO 4 , NO 3 , and NH 4 is attributed to anthropogenic air pollution. The enrichment factors of SO 4 , HCO 3 , K, Mg, and Ca suggested that their non-marine contribution ranges from 75.4% to 99.98%. However, the sea salt contributed substantially to Cl concentration up to 73.5%. Most of the rainwater parameters generally decreased with time and they were generally stabilized after 20 min, which is an effect of the first flush and thus some diversion (rerouting) is required for suitable artificial injection of the harvest rainwater in this study area.