Bimodal volcanism associated with early phases of Huronian rifting in central Ontario, dated about 2450 Ma, produced low-Ti tholeiitic basalts and two varieties of crustally derived calc-alkaline rhyolite. Early tholeiites are characteristically highly evolved, have Mg* values from 30 to 50, and display pronounced enrichment in large-ion lithophile elements (LILE) and light rare-earth element (LREE) in comparison with modern oceanic basalts, fractionated heavy rare-earth element (HREE) patterns, and low Ti, Zr, P, Nb, Ba, and K abundances. Ti/Zr ratios rise progressively in early basalts and associated basaltic andesite fractionates from about 35 in early flows to 55 in central units. Late basalts also carry enriched LILE and LREE, but, in contrast to early types, have average Mg* values greater than 50 and lower rare-earth element (REE) abundances with flat HREE patterns. They also display negative Ba, Nb, and P anomalies on chondrite-normalized distribution diagrams, but lack low K, Zr, and Ti contents. Their Ti/Zr ratios of about 80 approach chondritic levels. Melting models suggest the differences are explained by lower degrees of fusion (as low as 10%) in a hydrated, LILE- and LREE-enriched peridotite during generation of the early basalts, leaving a residue containing appreciable garnet, amphibole, Ti oxides, zircon, and apatite.Erupted simultaneously with the basalts were two distinctive rhyolite types: (1) a low-LILE, high-LREE group (25% of analysed specimens), derived by −20% melting of granulitic siliceous tonalitic gneiss, presumably at deep crustal levels, and (2) a high-LILE, low-LREE group (75%), derived, probably at shallower levels, by ≤ 30% melting in granitic rocks with pegmatitic or leucogranitic compositions. Mutual magma mixing of basalts and rhyolites during early stages of volcanism produced abundant hybrid andesites, but the frequency of contamination is much lower in later units.Hypothetical subcontinental source compositions, calculated from the Raleigh equation, suggest that the Huronian mantle had already undergone a complex history. Low Ba, Nb, P, Ti, and depleted HREE abundances compared with abundances for modern oceanic basalts suggest that a basaltic melt had already been withdrawn from this source during Archean time. Subsequently, an episode of hydrous metasomatism enriched the source in LILE and LREE. The latter event resulted from (1) subcontinental mantle metasomatism by previous Archean subduction, (2) mantle metasomatism during the terminal Archean Kenoran Orogeny, or (3) a wave of hydrous metasomatism accompanying Huronian mantle convection immediately preceding volcanism.