Poly(acrylamide) (PAM) with configurational sequences was synthesized under ultraviolet (UV) catalyzed by Lewis acid (here yttrium salts) and in the presence of dibenzyl trithiocarbonate (DBTTC). DBTTC is selected as the photoinitiator and also the chain-transfer agent to achieve a living manner for the polymerization process. A series of PAMs with narrow molecular weight distributions and different configurational sequences have been prepared. The catalysis effects on configurational control of different contents of the yttrium salts have been studied.