Three "π"-shaped D-A-type thiodiazoloquinoxaline derivatives with different electronic structures and rotations have been prepared. Their particular structures allow these molecules to possess a broad absorption range and sufficient intramolecular motions, dissipating energy through a thermal deactivation pathway. Among the three materials, TPA-TQN showed the best steam generation efficiency (84.52%) and water-electricity cogeneration efficiency (63.95%). This study suggests that D-A structures with different electronic configurations, free rotors, and hydrophilicities make great contributions to the overall solar energy conversion performances.