We have developed a set of new multi-level electronic structure methods by including energies calculated from several density functional theory methods. The parameterization of the improved methods MLSE-DFT was based on updated databases of 109 atornization energies, 38 hydrogen-transfer barrier heights, and 22 neutral non-hydrogen-transfer reaction barrier heights. The best method, MLSE-TPSS1KCIS, performed impressively on the above three types of energies with mean unsigned errors of 0.62, 0.55, and 0.69 kcal/mol, respectively. We found that the hybrid versions of DFT are not absolutely necessary, and the performance can be improved significantly using two different basis sets in DFT calculation. (c) 2007 Elsevier B.V. All rights reserved.