Two kinds of artificial ligand of asialoglycoprotein receptor (ASGPR), galactosyl human serum albumin (Gal_nHSA) and galactosyl poly-L-glutamic acid (Gal_nPLGA), were synthesized chemically. IC₅₀ of synthetic ligands inhibiting the binding of ¹²⁵I-asialofetuin (¹²⁵I-ASF) to ASGPR of rat liver cell membrane were assayed. The results showed that Gal₁₂HSA, Gal₁₅HSA, Gal₂₆HSA, Gal₃₀HSA and Gal₃₄-PLGA could all efficiently inhibit the binding of ¹²⁵I-ASF to ASGPR. The affinities of Gal_nHSA increased along with the increase of the coupling number of galactosyl. Here, the synthesis and the affinity identification of Gal₃₄PLGA with ASGPR were firstly reported. These synthetic ligands with abundant sources and simple preparations may be used as targeting ligands for the liver-targeting delivery of drugs or genes.