We present a theoretical investigation of the influence of domain boundaries on the Ge/Si(111)-5 × 5 phase using both large-scale DFT simulations and an analytical model. It is shown that different boundary types modify the atomic and electronic structure of the adjoining 5 × 5 domains in very different ways. A simple theoretical model, that describes the energy interaction J between the boundaries and the 5 × 5 phase, is presented and the interaction energy decay J(x) ≈ x(-n) for different domain boundaries is estimated. Additionally, the influence of the boundaries on the atomic and electronic structure of adatoms in the parental 5 × 5 phase is analyzed and it is argued that the presence of domain boundaries may strongly affect not only the physical but also the chemical properties of the Ge/Si(111)-5 × 5 phase.