We report the discovery of unintentional phosphorus (P) doping when tri-n-octylphosphine (TOP) ligands are used in Ni nanoparticle synthesis, which is the most common method for monodisperse Ni nanoparticle synthesis. The nanoparticles appear pure face-centered cubic (fcc) Ni in X-ray diffraction despite the surprisingly high level (5 atomic %) of P. We find that the P doping follows a direct relationship with increased reaction time and temperature and that the P doping can be estimated with the degree of lattice expansion shown from a peak shift in the XRD spectrum. Through EXAFS modeling and density-functional (DFT) calculations of defect formation energies we find that the P atoms are preferentially located on the fcc lattice as substitutional dopants with oxidation state of zero. Magnetic and catalytic properties are shown to be greatly affected by this doping; DFT calculations show magnetization losses in the Ni system, as well as in Fe and Co systems. These findings are likely relevant for other metal syntheses that employ phosphine ligands.