We describe the ab initio construction of two-center tight-binding (TB) hamiltonians, which at a properly chosen input density upon non-selfconsistent solution of the related Kohn-Sham equations transform the energy within density-functional theory (DFT) into a tight-bindinglike expression. In cases, where the electron density of the interacting many-atom structure in good approximation may be represented as a sum of atomic-like densities, the method has been shown to operate highly transferable, being particularly successful in determining the properties of low-energy silicon clusters, in predicting the structure and vibrational signatures of fullerene oligomers, amorphous carbons and carbon nitrides and in simulating elementary growth reactions on diamond surfaces. The uncertainties within the standard non-SCF DF-TB-variant, however, increase if the chemical bonding is controlled by a delicate charge balance between different atomic constituents, as e.g. in organic molecules and in polar semiconductors. Therefore, we extend the standard TB-approach to the operation in a selfconsistent-charge mode (SCC-DFTB) in order to improve total energies, forces, and transferability in the presence of considerable long-range Coulomb interactions. By using a variational technique, we derive a transparent and readily calculable expression for the iterative modification of Hamiltonian matrix elements and show, that the final energy is a second order approximation to the total energy in density-functional theory, see M. Elstner et al., this Symposium. First successful applications to surface studies of GaAs and dislocation modeling in GaN will be presented.