The synthesis and self-organizing behaviour into liquid-crystalline mesophases of two libraries of segmented block co-dendrimers are described. The overall structure of the dendritic supermolecules consists of two chemically incompatible molecular moieties, covalently connected by combinatory cross-coupling reactions. One block is composed of linear perfluorinated segments (2 generations, defining the two libraries), and the bulky dendritic compartment is formed by a lipophilic poly(benzyl ether)-based dendron (3 generations). The mesomorphic properties were studied as a function of the respective generations of both blocks and of the peripheral alkyl chains’ substitution pattern. The results of these investigations reveal the formation of unusual and highly segregated supramolecular liquid-crystalline mesophases, whose arrangements are subtly controlled by the lipophilic/fluorophobic balance and dendritic connectivity.