Assembly processes can drive the selection of self-assembling molecules in dynamic combinatorial libraries, yielding self-synthesizing materials. We now show how such selection in a dynamic combinatorial library made from an amphiphilic building block which, by itself, assembles into micelles, can yield membranous aggregates ranging from vesicles to sponge phases. These aggregates are made from a mixture of unconventional surfactant molecules, showing the power of dynamic combinatorial selection approaches for the discovery of new, not readily predictable, self-assembly motifs.