A novel powdery polymer aerogel (PPA) with a hierarchical pore structure was prepared via hypercrosslinking of monodisperse poly(styrene-co-divinylbenzene) nanoparticles. Subsequently, the PPA was carbonized to obtain a powdery carbon aerogel (PCA) with a well-inherited pore structure and a much higher surface area (2354 m2 g-1). The PPA-coated and PCA-coated fibers were easily fabricated benefiting from the powdery morphologies of PPA and PCA, and demonstrated high extraction efficiencies towards hydrophobic analytes owing to their functional groups, unique three-dimensional (3D) porous nanonetworks and high surface areas.