Abstract: Heat exchange systems are provided that include one or more polymeric hollow fibers. Exemplary hollow fibers are asymmetric and include a microporous wall and a dense skin formed thereon, thereby preventing liquid transmission and/or contamination through the wall of the hollow fiber while simultaneously enhancing heat transfer based on the presence of liquid molecules within the porous substructure of the hollow fiber. The hollow fibers may be employed in a variety of heat transfer-related commercial/industrial applications, including solvent-aqueous systems, organic-aqueous systems, organic-organic systems, desalination applications, solar heating applications, applications in the chemical industry, applications in the biomedical industry, and applications in the biotechnology or pharmaceutical industry, e.g., extracorporeal blood oxygenation systems. Heat transfer systems wherein steam is advantageously condensed on a first side of a polymeric, hollow fiber-based heat exchanger are also provided.