First-principles density functional calculations are performed to study the adsorption behavior of Pt monolayer on the stoichiometric BiFeO3 (0001) polar surfaces. According to our results, the Pt monolayer adsorbed on the negative BiFeO3 (0001) surface behaves as a satisfactory epitaxial layer, while the Pt monolayer on the positive surface exhibits no epitaxial relation with the BiFeO3 substrate. In either case, the Pt adatoms can be classified into two types: One type is the Pt adatom which binds directly to the low-lying O anion and exhibits cationic feature, the other type of Pt adatom displays anionic character with Bi or Fe cation as its nearest neighbor. Besides the distinct charge transfer effect and orbital hybridization behavior, we also predict that these two types of Pt adatoms have different effects on the surface magnetic properties. Our results provide significant implications for the magnetoelectric devices and heterogeneous catalysis based on the metal/BiFeO3 interfaces. (C) 2017 Elsevier B.V. All rights reserved.