Alkynyl-substituted phenyldithiafulvenes have been found to act as versatile building blocks for the construction of π-conjugated molecular rods, shape-persistent macrocycles (SPMs), and conducting polymers. Through Cu(I)-catalyzed alkynyl homocoupling, a series of linear-shaped π-extended tetrathiafulvalene analogues (exTTFs) carrying conjugated oligoynes (ranging from diyne to hexayne) as the central π-bridge were readily prepared. The solid-state properties and reactivities of diyne- and tetrayne-centered exTTFs were characterized by X-ray crystallography and differential scanning calorimetry (DSC), while the electronic properties of the oligoyne-exTTFs were elucidated by UV-vis absorption spectroscopy and density functional theory (DFT) calculations. Cyclic voltammetric analysis showed that the terminal phenyldithiafulvene groups of the oligyne-exTTFs could undergo oxidative coupling to form tetrathiafulvalene vinylogue (TTFV)-linked polymer wires. Through a different synthetic route involving oxidative dimerization and Pd/Cu-catalyzed alkynyl homocoupling, the acetylenic phenyldithiafulvene precursors led to shape-persistent macrocycles where the formation of trimeric macrocycles was particularly favored due to the small ring strain incurred. Finally, spectroelectrochemical studies on these oligoyne and TTF hybrid materials disclosed electrochromic and molecular redox-controlled switching properties applicable to molecular electronic and optoelectronic devices.