A new series of extended dithieno[3,2-b:2',3'-d]phospholes with dendritic and non-dendritic architectures involving phenylenevinylene as well as Frechet-type dendrons is presented. Modification of the phosphorus center with Pd allows for the generation of a dimeric dendrimer with Pd-center. The synthetic strategy employed balances the rigid main scaffold with the flexibility of the dendrons in order to keep control of supramolecular self-organization features. All the structures show a high photoluminescence in both solution and solid state, which is further intensified via energy transfer from the dendrons to the core. In terms of self-organization in solution, three of the derivatives which bear an extended phosphole unit as common moiety are able to gel a variety of organic solvents at room temperature independently from the nature of their substituents. Notwithstanding, the dimeric dendrimer with Frechet-type dendrons is only able to display gel properties at low temperature. All gels exhibit pronounced photoluminescence properties that can be tuned by variation of the solvent and the temperature. In absence of solvent, the phosphole derivatives exhibit, moreover, liquid-crystalline mesomorphism features. While three of the compounds present stable and highly luminescent columnar hexagonal phases at room temperature, the fourth species was found to be crystalline in the thermal range up to its isotropic state. Finally as proof of concept, the multifunctionality of these materials is demonstrated in an electrochromic device.