The Toarcian oceanic anoxic event (~183 Myr ago) represents a global perturbation marked by increasing organic carbon burial and a general decrease in calcium carbonate production likely triggered by elevated carbon dioxide levels in the atmosphere. Here we present quantitative analyses of calcareous nannofossil diversity and abundance from the Castillo de Pedroso section in Cantabria, northern Spain. We compare these data with geochemical data (C and O isotopes) obtained from biogenic and bulk carbonate records in order to highlight the response of calcareous phytoplankton to major climatic and paleoceanographic changes. The Pliensbachian/Toarcian boundary is characterized by an abrupt decrease in abundance of Schizosphaerella punctulata, the most important lithogenic contributor to (hemi) pelagic carbonates in the Early Jurassic. The early Toarcian nannofloral assemblages show an increase in abundance of Mitrolithus jansae and small-sized r-selected taxa and a progressive decrease in S. punctulata percentages. The deep dwellers M. jansae and S. punctulata experienced a major crisis slightly prior to the deposition of the Toarcian black shales that are characterized by high abundances of eutrophic taxa such as Lotharingius spp. and Biscutum spp. The return of S. punctulata associated with lower percentages of eutrophic taxa was observed just above the Toarcian black shales. The Toarcian episode reveals that high CO2 levels and increasing primary productivity probably triggered a shift in abundance from highly calcified nannoliths such as S. punctulata and M. jansae to small-sized r-selected coccoliths that overall record a biocalcification crisis at the onset and during the Toarcian episode.