Nowadays asymmetric thin film composite (TFC) polymeric hollow fiber (HF) membranes are extensively used in industrial gas/vapor separations, water treatment etc. There are numerous advantages to use hollow fibers such as: low energy requirements, simplicity of operation, and high specificity. In the present article we discuss the progress made during the past decade in the preparation of the HF substrate and preparation/modification of the thin selective layer. Their applications in water treatment, dehydration of alcohols via pervaporation and gas/vapor separation are also demonstrated.