An efficient double Friedel‐Crafts alkylation strategy has been developed for the synthesis of 2,2‐bis(1,2,3,4‐tetrahydroquinolin‐6‐yl)acetates from N‐arylglycine esters using 10 mol‐% CuI in water as solvent. The reaction presumably involves α‐C‐H bond functionalization and concurrent nucleophilic substitution of the N‐arylglycine esters producing double Friedel‐Crafts alkylation products. The reaction protocol is successfully extended for N‐methyl aniline and indole nucleophiles.