Herein, bimetallic dendritic core-shell AuPd@Au nanocrystals (AuPd@Au NCs) were prepared by a simple one-pot aqueous method using xanthine as a green growth-directing agent. By virtue of the enhanced peak currents in the H2O2 reduction catalyzed by AuPd@Au NCs, a label-free immunosensor was constructed for the detection of prostate specific antigen (PSA). The immunosensor exhibited significantly improved analytical performance for the assay of PSA with wide linear range of 0.1–50ngmL–1 and low detection limit of 0.078ngmL–1 (S/N = 3), coupled with the improved stability, reproducibility and selectivity. It provides a promising platform for clinical research and diagnosis.