The asymmetric cross‐aldol reaction of dichloroacetaldehyde with aldehyde pronucleophiles proceeds in the presence of a trifluoromethyl‐substituted diarylprolinol to afford γ,γ‐dichloro‐β‐hydroxy aldehydes in good yield with excellent enantioselectivity. The obtained products are useful synthetic intermediates; they were successfully converted to form chiral alkynes and dichloroalkenes.