We studied the synthesis of original thiosugar scaffolds by enantioselective aldolization. L‐Proline‐catalyzed C–C bond formation was the key step in the synthesis of L‐erythro‐thioketoses (3S,4R), whereas fructose‐6‐phosphate aldolase‐catalyzed reactions yielded the D‐threo‐thioketose series (3S,4S). By the organocatalytic approach, 5‐thio‐L‐ribulofuranose (1) and 5‐deoxy‐6‐thio‐L‐psicopyranose (2) were obtained in satisfactory overall yields from 2‐haloacetaldehydes, whereas 5‐thio‐D‐xylulofuranose (3) was synthesized in 50 % overall yield by an enzymatic aldolization reaction in only two steps from the same starting material.