In this study, the Pd/BiF₃ thin films are successfully prepared by the facile in-situ electrochemical-photoreduction method from the Bi plates, and the photocatalytic performances of the BiF₃ thin films with different mass fractions of Pd are investigated for comparison. The Pd/BiF₃ thin films are characterized by the XRD, SEM, XPS and UV-Vis DRS methods. The photocatalytic performance of Pd/BiF₃ thin films is investigated with rhodamine B (RhB) as the photocatalytic degradation object. Our characterization results indicate that when the noble metal Pd is loaded uniformly on the surface of BiF₃ thin films and the mass fraction of Pd is 2.0%, the Pd/BiF₃ thin films exhibit the optimal photocatalytic activity and stability for the degradation of RhB. In addition, there exist an obvious redshift of optical absorption bands and a decrease of bandgap from 3.70 eV to 3.03 eV. The capture experiment of active species confirms that when the mass fraction of Pd is 2.0%, the roles of the ·OH, · O2- and h ⁺ are from large to small during the photocatalytic degradation of RhB by Pd/BiF₃ films. Finally, an enhancement mechanism of photocatalytic performance of Pd/BiF₃ thin films is proposed.