Soluble poly(ferrocenylenevinylene) (PFV) 6 was synthesized via ring-opening metathesis polymerization (ROMP) of ansa-(vinylene)ferrocene Fe(eta-C5H3'Bu)(2)C2H2 (5) with Bu-t substituents on the cyclopentadienyl (Cp) ligands. Monomer 5 was obtained through intramolecular dicarbonyl coupling of the corresponding ferrocene-dicarbaldehyde, 1,1'-di-t-butyl-3,3'-dicarbaldehyde, Fe(eta-(C5H3Bu)-Bu-t)(CHO)(2) (4) in the presence of the McMurry reagent. Both monomer precursor 4 and monomer 5 were structurally characterized by H-1 and C-13 NMR spectroscopy, X-ray crystallography, mass spectrometry, and elemental analysis. ROMP of 5 was investigated using molybdenum-based (Schrock-type) and ruthenium-based (Grubbs-type) initiators under various conditions and was monitored by 1H NMR spectroscopy. Soluble polymers with low or high molecular weight were obtained and completely characterized. Photolytic and thermal ring-opening polymerizations of 5 were also attempted, but only unreacted monomer was isolated under these conditions. The electronic structure of polymer 6 was explored using UV-vis spectroscopy, and evidence for moderate rather than extensive electron delocalization was revealed. Redox reversibility was probed by cyclic voltammetry (CV) for both monomer 5 and polymer 6. The electron-donating effect of the 'Bu groups substituted to the Cp ligands was signaled by the negative shift of the oxidation potentials, and the electronic interaction between the iron centers in the polymer backbone was also evaluated using CV.