Although high internal phase emulsion (HIPE)‐templating is promising to prepare macroporous materials (polyHIPEs) with controllable shapes and tuneable property, fibrous polyHIPEs with stretchability and their continuous preparation are still challe...
Although high internal phase emulsion (HIPE)‐templating is promising to prepare macroporous materials (polyHIPEs) with controllable shapes and tuneable property, fibrous polyHIPEs with stretchability and their continuous preparation are still challenging. Here, we report the fabrication of polyHIPE fibers in a continuous manner through wet spinning of HIPEs. The successful fabrication of polyHIPE fibers depends on HIPE dispersed phase fractions, ammonia‐catalyzed interfacial reaction and wet spinning. Dry polyHIPE fibers exhibit tunable diameters, hierarchically porous structures, high stability to temperature and to various solutions, and high stretchability (with a high tensile strain of 155%), which is hard to achieve for polyHIPEs. The polyHIPE fibers show enhanced uptakes to both water (14.4 ml g−1) and organic solvents (up to 26.3 ml g−1), and the amphiphilic swelling is rare for polyHIPEs. Moreover, the dry polyHIPE fibers show good thermal insulation, similar to that of cotton. Simple wet spinning, combining with HIPEs with tuneable composition, is promising for preparing various polyHIPE fibers for various potential applications.