The contribution of the Deccan Traps (west-central India) volcanism in the Cretaceous-Paleogene (KPg) crisis is still a matter of debate. Recent U-Pb dating of zircons interbedded within the Deccan lava flows indicate that the main eruptive phase (>1.1 × 106 km3 of basalts) initiated ∼250 k.y. before and ended ∼500 k.y. after the KPg boundary. However, the global geochemical effects of Deccan volcanism in the marine sedimentary record are still poorly resolved. Here we investigate the mercury (Hg) content of the Bidart (France) section, where an interval of low magnetic susceptibility (MS) located just below the KPg boundary was hypothesized to result from paleoenvironmental perturbations linked to the paroxysmal Deccan phase 2. Results show Hg concentrations >2 orders of magnitude higher from ∼80 cm below to ∼50 cm above the KPg boundary (maximum 46.6 ppb) and coincident with the low MS interval. Increase in Hg contents shows no correlation with clay or total organic carbon contents, suggesting that the Hg anomalies resulted from higher input of atmospheric Hg species into the marine realm, rather than organic matter scavenging and/or increased runoff. The Hg anomalies correlate with high shell fragmentation and dissolution effects in planktic foraminifera, suggesting correlative changes in marine biodiversity. This discovery represents an unprecedented piece of evidence of the nature and importance of the Deccan-related environmental changes at the onset of the KPg mass extinction.