We report SUPRAphos-based rhodium catalysts that are unusually regioselective in the hydroformylation of styrene at low temperatures (40 °C) producing mainly the linear aldehyde (72%). This ligand-specific phenomenon is observed for two rhodium catalysts with heterobidentate phosphine–phosphoramidite ligands. We propose that the high selectivity for the linear product is caused by enhanced β-hydride elimination, due to specific substrate–ligand interactions, most likely π–π interactions.