The development of new molecular topological conjugated configurations over Pd catalysts for C-C bond formation is an essential objective for material chemists and can be used extensively in optoelectronic devices such as chemical biosensing, OLED and organic photovoltaics. Here, we report the general twofold germinal C-C bond formation at 1,1-dibromoolefin via Suzuki or Stille cross-coupling reactions of aromatic boronic acid/ester over heterogeneous Pd catalysts. We employ a series of recipe from a library of precursors to produce conjugated macrocyclics, conjugated dendrimers, linear conjugated polymers and 2-3 dimensional conjugated covalent organic frameworks (COF). This generous strategy toward specific molecular topological conjugated configurations is highly efficient for coupling aryl bromides with various coupling partners with high activity and selectivity under mild conditions. The macrocyclics, dendrimers and 1-D polymers show feature molecular assembly and fluorescence properties. 2D and 3D covalent organic frameworks show great N2-adsorption and solvent-sensitive fluorescence.