Here we report original molecular vectors that ensure broad flexibility to tune the shape and surface properties of plasmid DNA (pDNA) condensates . The prototypic design involves a cyclodextrin (CD) platform bearing a polycationic cluster at the primary face and a doubly-linked aromatic module bridging two consecutive monosaccharide units at the secondary face, which behaves as a topology-encoding element . Subtle differences at the molecular level then translate into disparate morphologies at the nanoscale, including rods, worms, toroids, globules, ellipsoids and spheroids . In vitro evaluation of the transfection capabilities revealed marked selectivity differences as a function of nanocomplex morphology . Remarkably high transfection efficiencies were associated to ellipsoidal or spherical shapes with a lamellar internal arrangement of pDNA chains and CD bilayers . Computational studies support that the stability of such supramolecular edifices is directly related to the tendency of the molecular vector to form noncovalent dimers upon DNA templation . Since the stability of the dimers depends on the protonation state of the polycationic clusters, the co-aggregates display pH responsiveness, which facilitates endosomal scape and timely DNA release, a key step in successful transfection . The results provide a versatile strategy for the construction of fully synthetic and perfectly monodisperse non-viral gene delivery systems uniquely suited for optimization schemes.