The burgeoning interest in two-dimensional (2D) black phosphorus (bP) contributes to the expansion of its applications in numerous fields. In the present study, 2D bP is used as a support for homogeneously dispersed palladium nanoparticles directly grown on it by a wet chemical process. Electron energy loss spectroscopy–scanning transmission electron microscopy analysis evidences a strong interaction between palladium and P atoms of the bP nanosheets. A quantitative evaluation of this interaction comes from the X-ray absorption spectroscopy measurements that show a very short Pd–P distance of 2.26 Å, proving for the first time the existence of an unprecedented Pd–P coordination bond of a covalent nature. Additionally, the average Pd–P coordination number of about 1.7 reveals that bP acts as a polydentate phosphine ligand toward the surface of the Pd atoms of the nanoparticles, thus preventing their …