To understand the bioconcentration of methylmercury (MeHg) at the base of the riverine food chain, we determined levels of dissolved organic carbon, microseston, Hg, and MeHg in surface water in relation to the microzooplankton MeHg from Yeongsan River. The spatial distribution of unfiltered Hg (0.29-3.1 ng/L) and dissolved Hg (0.15-0.74 ng/L) closely followed the microseston distribution. The spatial distribution of unfiltered MeHg (0.0078-0.077 ng/L) and dissolved MeHg (0.0069-0.018 ng/L) increased with increasing distance from the river mouth and appeared to arise from the shallow wetlands surrounding the upper riverbanks and then to be transported downstream. The logarithm of the MeHg bioconcentration factor for microzooplankton ranged from 5.3 to 6.0 (5.7 ± 0.18), and for microseston ranged from 4.0 to 5.4 (4.9 ± 0.35). Linear correlation statistics comparing microzooplankton MeHg and river water characteristics revealed that microzooplankton MeHg concentration was most significantly correlated with unfiltered MeHg (r = 0.83) and particulate MeHg (r = 0.80) levels. This result suggests that MeHg in unfiltered river water, which is relatively easy to determine, can be used as a surrogate for MeHg in microzooplankton that may influence MeHg levels in higher-trophic-level organisms.