An effective Hamiltonian in a basis of spin- and space-symmetry adapted configuration state functions (CSF), which includes information from Kohn-Sham density functional theory (DFT), is used to calculate configuration interaction (CI) wave functions for the electronic states of molecules. The method emphasizes on states of multiconfigurational character which cannot be represented by conventional DFT. The CI matrix elements are constructed empirically by using the exact operator and corrections from DFT. Both the optimized KS orbitals from the parent determinant and the corresponding KS potential from the parent state density are used. Depending on their energy gap the CI off-diagonal elements between CSF are exponentially scaled to zero to avoid double counting of electron correlation. The selection of the most important CSF describing nondynamical correlation effects and the use of an approximate resolution of the identity (RI) for the evaluation of the two-electron integrals allows a very efficient DFT/MRCI treatment of molecules with several hundreds of electrons. As applications, the prediction of excitation energies for singlet and triplet states of organic molecules and transition metal complexes, the calculation of electronic circular dichroism spectra and investigations of the energetics of diradicals are presented. It is found, that the new DFT/MRCI approach gives results of high accuracy (rms errors for relative energies < 0.2 eV) comparable to those from sophisticated ab initio treatments.