The mineralogy and chemistry of picrites from Mauna Loa and Kilauea have been investigated to evaluate, for Hawaiian tholeiitic picrites, the contrasting genetic models which have been proposed for these Mg-rich volcanics, namely products of direct crystallization of high-Mg melts (20–25% MgO) or the result of accumulation of olivine phenocrysts into less Mg-rich melts. Genetic interpretations rely heavily on Mg-Fe partitioning relations between olivines and their picrite hosts. Although the 100 Mg/(Mg + Fe2+) ratios (M) of picrites are wide-ranging (M=73.6–82.9 for Fe2O3/FeO=0.15), with MgO as high as 27.8%, the average 100 Mg/(Mg+Fe) ratios (mg) of the cores of olivine phenocrysts (megacrysts) show only restricted compositional variation (mg=87.2–89.0). Successive olivine generations are progressively more Fe-rich. Olivine/liquid Mg-Fe partitioning data and the Mn and Ni abundances in olivine phenocrysts collectively indicate that they were precipitated by Mg-rich basaltic melts with 12–14% MgO. Spinel compositions range from liquidus magnesiochromites, occurring mainly as inclusions in olivine phenocrysts, to groundmass titanomagnetites which crystallized at nearsolidus temperatures. The Cr2O3 contents and M values of liquidus magnesiochromites suggest that their parent melts were neither Mg-rich picritic (MgO>20%) nor relatively Mg-poor basaltic types.