A chromophoric oligo(p-phenyleneethynylene) (OPE) bola-amphiphile with dioxyoctyl side chains (H2OPE-C-8) has been self-assembled with Cd-II to form a 1D coordination polymer, {Cd(OPE-C-8)(DMF)(2)(H2O)} (1), which is further interdigitated to form a 2D network. Such 2D networks are further interwoven to form a 3D supramolecular framework with surface-projected alkyl chains. The desolvated framework showed permanent porosity, as realized from the CO2 adsorption profile. 1 showed high water contact angles, ortraying its superhydrophobic nature. 1 also showed a linker-based cyan luminescence. Solvent removal led to a bathochromic shift in emission into the green region. Resolvation with N,N-dimethylformamide brought back the original cyan emission, whereas for tetrahydrofuran, ethanol, and methanol, it persisted at an intermediate state. Density functional theory calculations unraveled that, twisting of the OPE phenyl rings generated the red shift in emission.