A series of rigid pi-conjugated bis(terpyridines) (M1-M7) bearing electron-acceptor spacer units in 4'-position was synthesized in moderate to high yields by Pd-0-catalyzed Sonogashira cross-coupling reactions. The compounds were fully characterized by NMR spectroscopy, MALDI-TOF mass spectrometry, elemental analysis and their photophysical properties were discussed in detail. These new bis(terpyridines) were applied for the self-assembly reaction with Zn-II ions to form metallo-homo polymers (P1-P7). Broadened NMR signals and UV-vis titration experiments confirmed the successful polymerization. The electro-optical properties of the materials were investigated in detail. Band gaps up to 2.08 eV and bright blue to orange photoluminescence with quantum yields of 18 to 66% were observed strongly depending on the nature of the pi-conjugated bis(terpyridine) system. In combination with electron-donor ditopic terpyridine ligands (MD1 and MD2), two Zn-II random copolymers (R1 and R2) were synthesized. These materials were investigated by UV-vis absorption and photoluminescence experiments in dilute solution and in the solid state, prepared by spin-coating from DMF Solutions. Thereby, random copolymer R2 featured an energy transfer from the donor to the acceptor part in dilute solution.