An acetylenic phenyldithiafulvene was developed as a versatile synthon for diverse TTFV-based macromolecular scaffolds. Through different coupling reaction sequences, shape-persistent macrocycles and linear TTFV-embedded polymers have been obtained and thereafter characterized by spectroscopic and voltammetric analyses. The TTFV polymer thin films generated via electropolymerization of a dithiafulvenyl-end-capped diyne monomer showed promising prospects in electrochromic and redox switchable molecular devices.