A spectral representation for the isotropic part of the Coulomb collisional operator is given. The particle distribution function is expanded in a series of generalized Laguerre polynomials, and the Coulomb collisional operator is expressed in terms of the spectral amplitudes. When the spectral representation is applied to the Fokker–Planck equation, a system of coupled ordinary differential equations for the spectral amplitudes is obtained. The spectral coefficients related to the Coulomb operator are defined through recurrence relations, which we reduce to simplified form. This makes possible accurate and efficient analytical and numerical evaluations of the interaction matrices. The results presented can be used in analytical investigations of the properties of the Coulomb collisional operator as well as in numerical calculations for plasmas far from thermal equilibrium. The method can also be generalized to include angular dependencies for non-isotropic particle distributions.