Quasicrystals are long-range ordered and yet nonperiodic. This interplay results in a wealth of intriguing physical phenomena, such as the inheritance of topological properties from higher dimensions, and the presence of nontrivial structure on all scales. Here, we report on the first experimental demonstration of an eightfold rotationally symmetric optical lattice, realizing a two-dimensional quasicrystalline potential for ultracold atoms. Using matter-wave diffraction we observe the self-similarity of this quasicrystalline structure, in close analogy to the very first discovery of quasicrystals using electron diffraction. The diffraction dynamics on short timescales constitutes a continuous-time quantum walk on a homogeneous four-dimensional tight-binding lattice. These measurements pave the way for quantum simulations in fractal structures and higher dimensions.