The authors thank the Eastman Chemical Company for funding (LI, and later JAF) and permission to publish. The EPSRC (EP/M003868/1) is also acknowledged for funding (JAF).The hydroformylation of propene to give predominantly iso‐butanal has been achieved; class‐leading selectivity is possible even at higher temperatures that deliver fast conversion. Racemic rhodium complexes of bidentate phospholane phosphites derived from tropos‐biphenols and unusual solvent systems are the key to the selectivity observed.PostprintPeer reviewe