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Subaqueous eruptions alter the chemical conditions of the lake by intensifying the interaction between hot volcanic rocks and water, resulting in the exchange of alkalis. The lower part of the Fengcheng Formation in the Mahu Sag, NW China, has abundant rhyolitic welded tuff and related pyroclastic deposits, which were deposited under ancient alkaline lacustrine deposits of the Fengcheng Formation. Despite this, the effect of the eruption process on the formation of the alkali lake remains unclear. To gain a better understanding of the eruptive behaviour and emplacement processes, detailed drilling core descriptions, microscopic observations, and interpretations of textural characteristics of rhyolitic welded tuff units and adjacent volcano‐sedimentary associations have been conducted. The rhyolitic welded tuff can be categorized into seven lithofacies units based on the degree of welding, devitrification characteristics, pore development, and filling characteristics. The age of eruption was determined through zircon U–Pb dating of the rhyolitic welded tuff, revealing it to be approximately 300 Ma, thereby providing constraints on the deposition time of alkaline lacustrine deposits. Mudstones that encase the welded tuff unit and quenched structures such as perlitic fractures, quench cracks of spherulite and lithophysae, and chalcedony spherules indicate that the welded tuff unit was formed through subaqueous eruption. Alkali fractionation (sodium and potassium) occurs in the spherulite and lithophysae zone and at the top condensation boundary, demonstrating that the subaqueous eruption process significantly enhanced devitrification and hydration, causing sodium to escape from the welded tuff and released into the lake water as sodium ions. The rhyolitic welded tuff provides evidence of the evolution of a subaqueous felsic eruption where the water‐rock reaction played a fundamental role in alkalizing the lake by providing the lake with sodium ions in Mahu Sag.