Tripodal N-methylated(1,3,5-benzene-tricarboxamide)-tris(phenylurea) BTA ligands, possessing urea functionalities in the meta position, are able to form extended self-assembly 2D networks via hydrogen bonding templated by sulfate (SO 4 2À ). Studies in solution and in the solid state, as well as scanning electron microscopy (SEM) on the self-assembly properties of the ligands showed that the convergence also leads to the formation of hierarchical structures, including porous films and spherical nano-sized particles, with the morphological outcome being highly solvent dependent.