Silicate glasses have no long-range order and exhibit a short-range order that is often fairly similar to that of their crystalline counterparts. Hence, the out-of-equilibrium nature of glasses is largely encoded in their medium-range order. However, the ring size distribution—the key feature of silicate glasses’ medium-range structure—remains invisible to conventional experiments and, hence, is largely unknown. Here, by combining neutron diffraction experiments and force-enhanced atomic refinement simulations for two archetypical silicate glasses, we show that rings of different sizes exhibit a distinct contribution to the first sharp diffraction peak in the structure factor. On the basis of these results, we demonstrate that the ring size distribution of silicate glasses can be determined solely from neutron diffraction patterns, by analyzing the shape of the first sharp diffraction peak. This method makes it possible to uncover the nature of silicate glasses’ medium-range order.