Solid phase extraction devices including a plurality of packed nominally aligned capillary-channeled polymeric fibers for use as stationary phase materials are disclosed. A plurality of fibers are packed together in a casing so as to provide good flow characteristics through the fibers and high surface area contact between a sample and the fibers. Different polymer compositions of the fibers permit the "chemical tuning" of the extraction process. The fibers can be physically or chemically derivatized to target specific analytes for separation from a test sample. Use of the fibers allows a wide range of liquid flow rates with very low backpressures. The fibers are easily packed into a micropipette tip or a conduit for use with a fluid flow device such as an aspirator or a pump. The devices can be used for isolation and pre-concentration of analytes from samples, for instance for proteins from buffer solutions or extraction of pollutants from remote locations.