Although the rarity of organofluorines in nature has long driven a large gap between the fields of fluorine chemistry and biocatalysis, the repurposing of promiscuous enzymes to elaborate simple fluorinated precursors has proven to be an attractive strategy to bridge this gap. We have shown that a pyruvate aldolase from the type II HpcH/HpaI family, which evolved to cleave pyruvate off from highly polar carbohydrate metabolites in vivo, can be engineered for remarkable substrate scope in the synthetic aldol direction. Secondary fluoride stereocenters are obtained from the addition of fluoropyruvate to a wide variety of polar, nonpolar, aliphatic, aromatic, and heteroaromatic aldehydes. Tertiary fluoride stereocenters, which have hitherto not been synthesized with biocatalytic carboligation, are obtained with readily synthesized ß-fluoro-α-ketoacid precursors and HpcH aldolase variants engineered for steric relief.