Commercial membranes today are manufactured from a handful of membrane materials. While these systems are well-optimized, their capabilities remain constrained by limited chemistries and manufacturing methods available. As a result, membranes cannot address many relevant separations where precise selectivity is needed, especially with complex feeds. This constraint requires the development of novel membrane materials that offer customizable features to provide specific selectivity and durability requirements for each application, enabled by incorporating different functional chemistries into confined nanopores in a scalable process. This study introduces a new class of membrane materials, amphiphilic polyelectrolyte complexes (APECs), comprised of a blend two distinct amphiphilic polyelectrolytes of opposite charge that self-assemble to form a polymer selective layer. When coated on a porous support from a mixture in a nonaqueous solvent, APECs self-assemble to create ionic nanodomains acting as water-conducting nanochannels, enveloped within hydrophobic nanodomains, ensuring structural integrity of the layer in water. Notably, this approach allows precise control over selectivity without compromising pore size, permeability, or fouling resistance. For example, using only one pair of amphiphilic copolymers, sodium sulfate rejections can be varied from >95% to <10% with no change in effective pore size and fouling resistance. Given the wide range of amphiphilic polyelectrolytes (i.e., combinations of different hydrophobic, anionic, and cationic monomers), APECs can create membranes with many diverse chemistries and selectivities. Resultant membranes can potentially address precision separations in many applications, from wastewater treatment to chemical and biological manufacturing.