The Valanginian stage (Early Cretaceous) includes an episode of significant environmental changes, which are well defined by a positive δ13C excursion. This globally recorded excursion indicates important perturbations in the carbon cycle, which has tentatively been associated with a pulse in volcanic activity and the formation of the Paraná-Etendeka large igneous province (LIP). Uncertainties in existing age models preclude, however, its positive identification as a trigger of Valanginian environmental changes. Here we report that in Valanginian sediments recovered from a drill core in Wąwał (Polish Basin, Poland), and from outcrops in the Breggia Gorge (Lombardian Basin, southern Switzerland), and Orpierre and Angles (Vocontian Basin, SE France), intervals at or near the onset of the positive δ13C excursion are significantly enriched in mercury (Hg). The persistence of the Hg anomaly in Hg/TOC, Hg/phyllosilicate, and Hg/Fe ratios shows that organic-matter scavenging and/or adsorbtion onto clay minerals or hydrous iron oxides only played a limited role. Volcanic outgassing was most probably the primary source of the Hg enrichments, which demonstrate that an important magmatic pulse triggered the Valanginian environmental perturbations.