In the present work, we have studied from a theoretical perspective the geometry and electronic properties of 2,2′-bithiophene (BT) and its derivatives 3,4′-alkyl-2,2′-bithiophene (3,4′ABT) and 3,4′-alkoxy-2,2′-bithiophene (3,4′OABT). Properties such as planarity, bond lengths, electron density, highest occupied molecular orbital → lowest unoccupied molecular orbital (HOMO → LUMO) excitation energy and π-delocalization energy, which are related to the electrical conductivity, were calculated and analyzed as a function of both the nature and length of the substituent. The oxidation process was also studied for the single-polaronic state. The ionization potential and the intramolecular reorganization energy were calculated following the semiclassical Marcus treatment. As a conclusion, the introduction of alkoxy chains in 3,4′-positions improves the electrical properties with respect to the bithiophene molecule and the corresponding alkyl derivatives.