A novel enantioselective aminomethylation reaction of diazo compound, alcohol and a-aminomethyl ether enabled by asymmetric counteranion-directed catalysis is disclosed that offers an efficient and convenient access to furnish optically active alpha-hydroxyl-beta-amino acids in high yield with high to excellent enantioselectivities. Control experiments and DFT calculations indicate that the transformation proceeds through trapping the in situ generated enol intermediate with methylene iminium ion, and the asymmetric induction was enabled by chiral pentacarboxycyclopentadiene anion via H-bonding and electrostatic interaction.