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A methodology for the asymmetric peroxidation of γ,δ-unsaturated β-keto esters is presented. Using a cinchona-derived organocatalyst, the target δ-peroxy-β-keto esters were obtained in high enantiomeric ratios of up to 95:5. Additionally, these δ-peroxy esters can be readily reduced to chiral δ-hydroxy-β-keto esters without impacting the β-keto ester functionality. Importantly, this chemistry opens up a concise route to chiral 1,2-dioxolanes, a common motif in many bioactive natural products, via a novel P₂O₅-mediated cyclisation of the corresponding δ-peroxy-β-hydroxy esters.