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Recently, the continuous tube-in-tube reactor based on the Teflon AF membrane is emerging as a powerful toolkit for accelerating gas-liquid mass transfer and reaction rate. Because of its large gas-liquid interfacial area and short mass transfer distance, the reactor can allow a fast gas-liquid mass transfer without direct contact between gas and liquid phases, offering an efficient and safe platform for implementing gas-liquid reaction and rapid determination of gas-liquid parameters. In this review, a detailed description and construction method of this reactor are provided. Then, the recent advancements of the tube-in-tube reactor in fundamental studies and practical applications in gas-involved chemical reactions and biosynthetic processes are discussed. Finally, a perspective on future potential applications of such flow reactors is provided.