Quantitatively accurate tight-binding parameters can be created from DFT band structures using Maximally Localized Wannier Functions, faster and for more complex materials than with fitting procedures. We propose a tight-binding parameter building block system for graphene that encapsulates defects like edges and missing atoms for reuse in bigger structures. We illustrate the concept for graphene nanoribbons. Towards a tight-binding description of the graphene-Ni interface, we show that Wannier orbitals can accurately reproduce the complicated band structure of a graphene-Ni slab. Additionally, we explore methods to extract tight-binding parameters from high-level quantum chemistry calculations and calculate Hartree-Fock expectation values of natural orbitals of acenes.