The organophosphorus radicals have drawn much attention in organic chemistry, biological processes, and functional materials due to their high reactivity. Although various species of organophosphorus radicals in solution have been observed by EPR spectroscopy, only a few examples have been isolated in the solid state. By using suitable bulky substituents, isolation of organophosphorus radicals such as dialkylphosphinyl radical, triarylphosphine radical cation, and tetraaryldiphosphine radical cation were achieved. The EPR spectra of those radicals showed the spin density of their radicals are mainly localized on phosphorus atom.