Solid-state interfaces play a major role in a variety of material properties. They are especially important in determining the behavior of nano-structured materials, such as metallic multilayers. However, interface structure and properties remain poorly understood, in part because the experimental toolbox for characterizing them is limited. Neutron reflectometry (NR) offers unique opportunities for studying interfaces in metals due to the high penetration depth of neutrons and the non-monotonic dependence of their scattering cross-sections on atomic numbers. We review the basic physics of NR and outline the advantages that this method offers for investigating interface behavior in metals, especially under extreme environments. We then present several example NR studies to illustrate these advantages and discuss avenues for expanding the use of NR within the metals community.