With the development of stable, compact and reliable pulsed laser sources the field of characterizing materials through their nonlinear optical response has bloomed. Second harmonic generation by non-centrosymmetric crystal structures has provided a new spectroscopic tool of potentially great utility in the pharmaceutical field. The nonlinear optical response of various materials provides a very sensitive technique for the characterization of pharmaceutically interesting bulk compounds and dispersions, and determining their concentrations. This work has potential application for in-line monitoring and quality control of pharmaceutical manufacturing. In this article we have presented an extensive review of the spectroscopic techniques that make use of the nonlinear optical response of solid media. Also, we have presented the results of our own work in this field.