The use of biocatalysts is continuing to grow and play an important role in the fine chemical and pharmaceutical industries, providing a sustainable and green synthetic strategy for the preparation of high-value chemicals. They have significant potential compared to traditional organic chemistry strategies, avoiding the use of expensive chiral ligands, toxic or rare transition metals, toxic solvents or extreme temperatures and pressures. Biocatalysts are also typically employed under mild reaction conditions in aqueous media, giving excellent chemo-and stereoselectivities. To date, the use of enzymes to generate sp 3 fluorine centers from non-chiral starting materials is limited, with early examples using aldolases to produce fluoroalcohols. A more recent approach used a cyclohexanone monooxygenase (CHMO) under anerobic conditions and light activation, to achieve a photoinduced reductive dehalogenation via an electron transfer mechanism (Scheme 1a). While cyclic substrates gave products in high enantiopurity (enantiomeric ratio, er) poor enantiocontrol was observed with an acyclic substrate. A non-haem iron enzyme has also been reported for enantioselective C(sp 3 )-F bond formation via radical fluorine transfer. However, fluorination was limited to the benzylic positions of ortho-arylamides. Ene reductases (EREDs) are flavin-containing enzymes that reduce alkenes activated with an electron-withdrawing group, via a trans-hydrogenation. The predominant family of EREDs is the old yellow enzyme (OYE) nicotinamide NAD(P)H dependent oxidoreductases which catalyze the reduction of α,β-unsaturated compounds including ketones, aldehydes, and nitro compounds; esters and acids are less readily accepted. In recent years many EREDs have been described, including some that can accept sterically challenging enones which were recently discovered in our laboratory via a sequence-based functional metagenomics strategy. EREDs have been applied in the synthesis of industrially useful compounds such as pregabalin precursors, flavor precursor molecules and other high value chiral building blocks on an industrially relevant scale. Interestingly, Hyster et al. have recently reported a single example of a fluoroalkene photoenzymatic radical cyclisation using an ERED (Scheme 1b) and a single example of the ERED photocatalyzed coupling of an α,α-chlorofluoroamide with styrene (Scheme 1c). However, no routes have been described to single isomer C(sp 3 )-F centers using bioreduction strategies of fluoroenones/enoates. EREDs have been shown