Abstract In this work, 2,2′-biphenol-based prolinamide water-compatible C 2- and C 1-symmetrical organocatalysts were synthesized with the use of enantiopure N-Cbz-(S)-proline as chiral source. Under the optimal reaction conditions, the C 1-symmetrical organocatalyst performed efficiently in the direct aldol reactions in water, thus delivering the desired aldol adducts in high yields (up to 100% yield) with excellent stereocontrol (up to 97:3 dr and 98% ee). The observed stereochemical outcome of the direct aldol reactions in water was interpreted by the proposed transition state.