Two series of 4,6-diamino-1,3,5-triazine triblock polyphiles consisting of an extremely long bisthiophene/triazole based rigid cores, with flexible alkyl chains at one end and a polar 4,6-diamino-1,3,5-triazine at the other end were synthesized. Colhex/p6mm mesophases were displayed by all bisthiophene based 4,6-diamino-1,3,5-triazine derivatives, whereas both Colhex/p6mm and CubI/Pm3¯n mesophases could be formed by corresponding triazole based 4,6-diamino-1,3,5-triazine derivatives. Evidence for the formation of the extra H-bonding between central triazole units and terminal 4,6-diaminotriazine groups which was responsible for the formation of cubic phases in triazole based compounds was obtained based on FT-IR measurements. Additionally, these triblock polyphiles can form organogels with interesting morphologies in different solvents. The influence of the alkyl chain length and the polarities of the heterocycles (bisthiophene/triazole) on the self-assembly of these compounds was systematically studied. Finally, these triblock polyphiles showed dual selectivities towards Pb2+ and Fe3+ ions.