The scope for biocatalytic modification of non‐native terpenone derivatives for speciality intermediates has hitherto been limited. Additionally, caprolactones are important feedstocks with diverse applications in the polymer industry and new non‐native terpenone‐derived biocatalytic caprolactone syntheses are of potential value for industrial biocatalytic materials applications. Biocatalytic reduction of synthetic analogues of R‐(–)‐carvone with additional substituents at C3 or C6, or both C3 and C6, using three types of OYEs (OYE2, PETNR and OYE3) shows significant impact of both regio‐substitution and the substrate diastereomer. Bioreduction of (–)‐carvone derivatives substituted with a Me and/or OH group at C6 is highly dependent on the substrate diastereomer. The products of bioreduction were efficiently biotransformed by Baeyer‐Villiger monooxygenase (BVase), CHMO_Phi1, provides a biocatalytic entry to new trisubstituted chiral caprolactones with complete regioselectivity. This provides both new non‐native polymerization feedstock chemicals, but also with enhanced efficiency and selectivity over native (+)–dihydrocarvone Baeyer‐Villigerase expansion, Optimum enzymatic reactions were scaled up to 60‐100 mg, demonstrating the utility for preparative biocatalytic synthesis of both new synthetic scaffold‐modified dihydrocarvones and efficient biocatalytic entry to new chiral caprolactones, which are potential single isomer‐chiral polymer feedstocks.