The present invention relates to the fields of chemistry and biology and more particularly to the field of biomaterials. The present invention includes amphiphilic fibers and membranes, which can be used for biomembranes and biocompatible devices. The present invention also relates to processes for preparing amphiphilic fibers and membranes from solutions comprising amphiphilic molecules. More particularly, the present invention relates to processes for preparing fibers and membranes from electrospinning solutions comprising amphiphilic molecules. The present invention further provides fibers and nonwoven membranes comprising amphiphilic fibers chosen from anionic surfactants, cationic surfactants, nonionic surfactants, phospholipids, sulfobetaines, lyotropic liquid crystalline molecules, and/or block copolymers. Electrospun fibers offer the potential for direct fabrication of biologically based, high-surface-area membranes without the use of multiple synthetic steps, complicated electrospinning designs, or post-processing surface treatments. Polymeric phospholipids, for example, have been shown to be attractive candidates for blood purification membranes, artificial heart valves and organs, and other prosthetics, including other biocompatible devices.