ESTIMATES of the MgO content of primary Hawaiian tholeiitic melts range from 8wt% to as high as 25wt% (refs 1, 2). In general, these estimates are derived from analysis of the whole-rock composition of lavas, coupled with the compositions of the most magnesian olivine phenocrysts observed. But the best estimate of magma composition comes from volcanic glass, as it represents the liquid composition at the time of quenching; minimal changes occur during the quenching process. Here we report the discovery of tholeiitic basalt glasses, recovered offshore of Kilauea volcano, that contain up to 15.0 wt% MgO. To our knowledge, these are the most magnesian glasses, and have the highest eruption temperatures (??? 1,316 ??C), yet found. The existence of these picritic (high-MgO) liquids provides constraints on the temperature structure of the upper mantle, magma transport and the material and thermal budgets of the Hawaiian volcanoes. Furthermore, picritic melts are affected little by magma-reservoir processes, and it is therefore relatively straightforward to extrapolate back to the composition of the primary melt and its volatile contents.