A series of main-chain metallopolymers (P1-P10) was prepared by the self-assembly of rigid-linear pi-conjugated bis(terpyridine) monomers (1-10) with Zn-II ions and was fully characterized. The polymerization was additionally confirmed by UV/vis titration experiments. A strong increase in viscosities (around 1.6 times) relative to those of the monomer solutions was found. The thermal stability of P1-P10 compared with that of 1-10 was enhanced as a result of the metallopolyrnerization. The electro-optical properties of the materials were investigated in detail. Tuning of the electrochemical and photopbysical properties was enabled; thus, bright purple to green photoluminescent (PL) emission (PL quantum yields of 0.12-0.81) for P1-P10 was observed in solution with the emission color strongly depending on the nature of the pi-conjugated bis(terpyridine) system. Thin homogeneous films of P6 were prepared by solution processing, that is, spin-coating and inkjet-printing, and exhibited intense yellow PL emission in the solid state. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4083-4098, 2009