The enantioselective protonation of prochiral enolates is an ideal and straightforward platform to synthesize stereodefined α-tertiary esters, which are recurring motifs in a myriad of biorelevant molecules and important intermediates thereof. However, this approach remains onerous, particularly when dealing with α-unactivated esters and related acids, as enantioinduction on the nascent nucleophile necessitates peremptory reaction conditions, thus far only achieved via preformed enolates. A complementary and contra-thermodynamic catalytic strategy is herein described, where a transient photoenol, in the form of a ketene hemiacetal, is enantioselectively protonated with a chiral phosphoric acid (CPA). The prochiral photoketene hemiacetals are procured from excited