Poly(thienylene vinylene)s (PTVs) are a unique class of low bandgap conjugated polymers that have received relatively little attention in organic electronic applications due to the limitations in conventional synthetic methodologies that are not capable to produce PTV structures beyond the rudimentary forms. We report here facile synthetic methods, combining acyclic diene metathesis (ADMET) and postpolymerization modification reactions, toward a series of structurally diverse PTVs. Specifically, halogen substituents including F, Cl, Br, and I, and conjugated thienyl groups bearing different substituents, have been installed onto every thiophene unit along the PTV backbones. While halogen substitution lowers both the HOMO and LUMO energy levels of the polymers, the overall optical properties are similar to the conventional unsubstituted PTVs. On the other hand, with increasing sizes of halogen atoms, the polymer crystallinity decreases caused by steric hindrance induced main-chain nonplanarity as suggested by density functional theory (DFT) calculations and confirmed by X-ray diffraction (XRD) and absorption measurements. With the cross-conjugated thienyl side-chains, the PTV polymers are all amorphous due to the large dihedral angles between the main-chain and side-chain thienyl rings. However, with strongly electron-withdrawing groups attached on the side-chain thiophene rings, new electronic transitions located at lower energies are observed, which have never been observed in PTVs and are assigned to main-chain to side-chain intramolecular charge transfer (ICTs) transitions. Such ICT transitions can potentially alter the PTV excited states ordering and dynamics, as evidenced by the appearance of fluorescence in one of the cross-conjugated PTVs bearing strong electron-withdrawing cyanoester vinylene groups. Applications of these new PTVs in bulk heterojunction (BHJ) organic solar cells (OSCs) have been attempted, and preliminary results showed Much improved performances over devices using conventional PTVs, especially for those applying the cross-conjugated PTVs. Our methodologies are highly versatile in preparing PTVs with systematically varied structures that for the first time provide means to study and gain better understandings on the structure-property relationships of this unique class of materials and to potentially generate, novel polymers tailor-designed for specific electronic applications.