We introduce a family of all-electron Gaussian basis sets, augmented MOLOPT, optimized for excited-state calculations on large molecules. We generate these basis sets by augmenting existing STO-3G, STO-6G, and MOLOPT basis sets optimized for ground state energy calculations. The augmented MOLOPT basis sets achieve fast convergence of GW gaps and Bethe–Salpeter excitation energies, while maintaining low condition numbers of the overlap matrix to ensure numerical stability. For GW HOMO–LUMO gaps, the double-ζ augmented MOLOPT basis yields a mean absolute deviation of 60 meV to the complete basis set limit. The basis set convergence for excitation energies from time-dependent density functional theory and the Bethe–Salpeter equation is similar. We use our smallest generated augmented MOLOPT basis (aug-SZV-MOLOPT-ae-mini) to demonstrate GW calculations on nanographenes with 9224 atoms requiring only 34300 core hours of computational resources.