Basaltic glass grains from the submarine south flank of Kı̄lauea, Hawai′i, have Cl concentrations of 0.01–1.68 wt%, the latter being the highest Cl content yet recorded for a Hawaiian glass. The high-Cl glass grains are products of brine assimilation by tholeiite magma. The glasses are grains in a sandstone clast from bedded breccias draping the southwestern margin of Kı̄lauea’s submarine midslope bench. The clast contains two distinct suites of glass grains: abundant degassed tholeiites, perhaps derived from subaerial lavas of Mauna Loa that shattered upon ocean entry, and a smaller population of Kea-type tholeiite (n=17 analyzed) that erupted subaqueously, based on elevated S (780–1050 ppm), H₂O (0.42–1.27 wt%), and CO₂ (<30–120 ppm), probably early in Kı̄lauea’s shield-building stage. Ten grains in this group have Cl>1000 ppm, six >5000 ppm, and two grains have >10 000 ppm dissolved Cl. Abundances of H₂O, Na₂O, K₂O, and several trace elements increase regularly with Cl concentration, and we estimate that Cl enrichment was due to up to 13 wt% addition of a brine consisting of 78% H₂O (wt), 13% Cl, 4.4% Na, 2.6% K, 2.6% Ca, 620 ppm Ba, 360 ppm Sr, 65 ppm Rb, and 7 ppm Pb. The large amounts of brine addition argue against bulk assimilation of low-porosity brine-bearing rock. The brine’s composition is appropriate for a seawater-derived hydrothermal fluid that reacted with basaltic wall rocks at T>100°C, losing Mg and S and gaining K, Ca, Rb, Ba, Sr, and Pb, followed by phase separation near 500°C and ∼50 MPa (5 km below sea level at hydrostatic pressure). Brine was assimilated at or near the depth it formed, as estimated on petrologic grounds, but under lithostatic conditions. The highest extents of assimilation either forced volatile saturation of the magma or enriched already coexisting magmatic vapor in H₂O. Possible mechanisms for assimilation are: (1) forcible injection of brine into magma during bursting of overpressured pockets heated by new dikes, or (2) intrusion of magma into lenses or sills occupied by trapped brine.