Substantially or roughly spherical micellar structures useful in the formation of nanoporous materials by templating are disclosed. A roughly spherical micellar structure is formed by organization of one or more spatially unsymmetric organic amphiphilic molecules. Each of those molecules comprises a branched moiety and a second moiety. The branched moiety can form part of either the core or the surface of the spherical micellar structure, depending on the polarity of the environment. The roughly spherical micellar structures form in a thermosetting polymer matrix. They are employed in a templating process whereby the amphiphilic molecules are dispersed in the polymer matrix, the matrix is cured, and the porogens are then removed, leaving nanoscale pores.