The synthesis of a class of highly pi-extended tetrathiafulvalene derivatives (1a and 1b) was explored using Sonogashira macrocyclization as a key step. The solid-state structure of 1b was characterized by X-ray single crystallography, showing a substantially bent, S-shaped molecular backbone and an ordered packing geometry in a pi-alkyl-alkyl-pi stacking fashion. Electronic and redox properties of 1b were investigated by UV-vis absorption, fluorescence spectroscopy, and cyclic voltammetry.