The pseudospectral (PS) method for self-consistent-field calculations is extended for use in generalized valence-bond calculations and is used to calculate singlet–triplet excitation energies in methylene, silylene, and ethylene molecules and bond dissociation and twisting energies in ethylene. We find that the PS calculations lead to an accuracy in total energies of ≤0.1 kcal/mol and excitation energies to ≤0.01 kcal/mol for all systems. With effective core potentials on Si, we find greatly improved accuracy for PS.