We have recently presented a real-space method for electronic-structure calculations of periodic systems that is based on the Hohenberg–Kohn–Sham density-functional theory. The method allows the computation of electronic properties of periodic systems in the spirit of traditional plane-wave approaches. In addition, it can be implemented efficiently on parallel computers. Here we will show that the method’s inherent parallelism, in conjunction with a newly designed approach for solving the Kohn–Sham equations, enables the accurate study of the ionic and electronic properties of periodic systems containing thousands of atoms from first principles.