AbstractThis study presents the synthesis, the spectroscopic and electrochemical properties of new bis‐ and tetra‐substituted azaboron‐dipyrromethene (aza‐BODIPY) dyes substituted by different electron donating groups connected to the aza‐BODIPY core through a thiophene unit. In line with theoretical calculations, experimental measurements point out the positive impact of the thiophene group that behave as a secondary donor group leading to an enhancement of the intramolecular charge transfer process in comparison to previously reported aza‐BODIPY dyes. This heterocycle has also been found to tune the oxidative potential and to stabilize the electro‐generated species.