Abstract A straightforward method to access novel families of enantioenriched cis‐ monofluorinated carbocyclic alcohols has been developed through ATH/DKR in up to 97 % yield, up to 99 : 1 dr and enantioinductions up to 97 % ee. Trans ‐difluorinated indans, tetrahydronaphthalenes, tetrahydroquinolines and chromans have been synthesized as well by deoxofluorination of the corresponding cis ‐fluoro alcohols. The reaction was performed on a series of variously substituted 3‐fluorochromanols, 3‐fluorotetrahydroquinolinols, 2‐fluoro inden‐1‐ols and 2‐fluoro 1,2,3,4‐tetrahydronaphthalen‐1‐ols in up to 86 % yields, with diastereoselectivities up to 97 : 3 and enantioselectivities up to >99 % ee.