We report herein the first examples of catalytic enantioselective synthesis of axially chiral 3-arylpyrroles. Reaction of a-isocyanoacetates with b-aryl-a,b-alkynic ketones in the presence of silver oxide and a phosphine ligand derived from Cinchona alkaloid occurred chemoselectively to afford enantioenriched 3-arylpyrroles in high yields with excellent enantiomeric excesses. The pyrrole ring was constructed de novo in this process.