β-Fluoromethyl (CH2F, CHF2, and CF3)-substituted chiral ketones are essential moieties and are vital building blocks in pharmaceutical and agrochemistry. However, general and convenient methods for enantio-diverse access to diverse β-fluoromethylated ketones are lacking, hindering the further development of these functional moieties. In this study, we developed an ene-reductase-based photobiocatalytic platform for efficient synthesis of enantio-divergent β-fluoromethylated chiral ketones. Our method highlights substrate-type diversity, excellent enantioselectivity, enzymatic enantio-divergent synthesis, as well as a dicyanopyrazine (DPZ)-type photosensitizer for biocompatible olefin E/Z isomerization in enzymatic stereoconvergent olefin asymmetric reduction, thereby providing a general photobiocatalytic solution to diverse β-fluoromethylated chiral ketones.