This paper presents a comprehensive review of the current state of knowledge of second harmonic generation (SHG) measurements, a subset of nonlinear ultrasonic nondestructive evaluation techniques. These SHG techniques exploit the material nonlinearity of metals in order to measure the acoustic nonlinearity parameter, β. In these measurements, a second harmonic wave is generated from a propagating monochromatic elastic wave, due to the anharmonicity of the crystal lattice, as well as the presence of microstructural features such as dislocations and precipitates. This article provides a summary of models that relate the different microstructural contributions to β, and provides details of the different SHG measurement and analysis techniques available, focusing on longitudinal and Rayleigh wave methods. The main focus of this paper is a critical review of the literature that utilizes these SHG methods for the nondestructive evaluation of plasticity, fatigue, thermal aging, creep, and radiation damage in metals.