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Thin film composite (TFC) polymeric hollow fiber (HF) membranes are widely used in industrial gas/vapor separations and water treatment. There are many advantages of TFC HF membranes, such as low energy requirements, simplicity of operation, and high specificity. In the present article, a review is made on the progress that has been achieved during the past 15 years in the preparation of the HF substrate and the preparation/modification of the thin selective layer. The review also includes their applications in water treatment, dehydration of alcohols via pervaporation, and gas/vapor separation.