A simple strategy for the synthesis of 5‐substituted‐3‐methylcyclohex‐2‐en‐1‐ones by proline‐catalyzed five‐step domino reactions of acetone and aromatic aldehydes is reported. The starting materials are stirred in the presence of L‐proline for 24 h then heated to 45 °C for a further 4‐6 h. The method can also be changed to exclusively form α,β‐unsaturated methyl ketones with >99 % E‐selectivity by heating the mixture to 80 °C in the second stage.