We examined the short-term toxicity of AgNPs and AgNO3 to Daphnia magna at sublethal levels using (1)H NMR-based metabolomics. Two sizes of polyvinylpyrrolidone-coated AgNPs (10 and 40nm) were synthesized and characterized and their Ag(+) release was studied using centrifugal ultrafiltration and inductively coupled plasma mass spectrometry. Multivariate statistical analysis of the (1)H NMR spectra showed significant changes in the D. magna metabolic profiles following 48h exposure to both AgNP particle sizes and Ag(+) exposure. Most of the metabolic biomarkers for AgNP exposure, including 3-hydroxybutyrate, arginine, lysine and phosphocholine, were identical to those of the Ag(+)-exposed groups, suggesting that the dominant effects of both AgNPs were due to released Ag(+). The observed metabolic changes implied that the released Ag(+) induced disturbance in energy metabolism and oxidative stress, a proposed mechanism of AgNP toxicity. Elevated levels of lactate in all AgNP-treated but not in Ag(+)-treated groups provided evidence for Ag-NP enhanced anaerobic metabolism. These findings show that (1)H NMR-based metabolomics provides a sensitive measure of D. magna response to AgNPs and that further targeted assays are needed to elucidate mechanisms of action of nanoparticle-induced toxicity.