Hydroxylamine (NH2OH) is an important intermediate of nitrification and can contribute to nitrous oxide (N2O) production through abiotic and biotic processes. NH2OH concentrations and associated biogeochemical controls in estuarine environments remain poorly understood. Here, we investigated spatial and seasonal variability of NH2OH concentrations in water and sediments, and determined the correlation between NH2OH concentration and N2O flux in Min River Estuary off southeast China. NH2OH concentrations in water and sediments varied from 0.22 to 140 nmol N L‒1 and from 0.17 to 9.22 μmol N kg‒1, respectively. NH2OH concentrations were significantly higher in warm than in cold seasons, suggesting that NH2OH production highly depends on temperature. Upper estuary (urban section) had higher NH2OH concentrations in water and sediments, followed by lower and middle estuary. Temperature, dissolved oxygen, and pH were the major drivers of spatial and seasonal variability in NH2OH concentrations. Water dissolved N2O concentrations and water-air N2O fluxes varied between 1.52 and 55.9 nmol N L‒1 and between ‒57.7 and 78.7 nmol N m‒2 h‒1, respectively, with switches from net sinks in spring season to net sources of N2O emissions in other seasons. N2O concentration and flux were observed to significantly correlate with NH2OH concentration, suggesting that NH2OH is an important contributor to N2O emissions. Although N2O concentrations and fluxes were linearly correlated with water NH2OH concentrations, the contribution of NH2OH to N2O production could not be addressed. Therefore, the dynamics of NH2OH concentrations are a useful tool to assess potential production and consumption pathways of N2O in estuarine and coastal ecosystems.