Nonorthogonal localized molecular orbital (NOLMO) is the most localized representation of electronic degrees of freedom.As such,NOLMOs are thus potentially most efficient for linear-scaling calculations of electronic structures for large systems.However,direct ab initio calculations with NOLMO has not been fully implemented and widely used,partly because of the slow convergence issue in the optimization of NOLMO.Toward realizing the potential of NOLMO for large systems,we applied an energy minimum variational principle for carrying out ab initio self-consistent-field (SCF) calculations with NOLMOs.We developed an effective preconditioning approach using the diagonal part of the second order derivatives and show that the convergence of the energy optimization is significantly improved.The speed of convergence of the energy and density are comparable with that of the conventional SCF approach,thus paving the way to the optimization of NOLMO in linear scaling calculations for large systems.