Direct organocatalytic asymmetric α-hydroxymethylation of ketones and aldehydes with formaldehyde has been developed, which furnished the corresponding α- hydroxymethylated adducts with high chemo-and enantioselectivity. The reaction is catalyzed by proline derivatives and is a simple method for the enantioselective synthesis of α-hydroxymethylated ketones and aldehydes, and C-2 symmetric diols.