In the presence of a sufficiently intense light, the optical properties of a polymer may become measurably nonlinear, leading to field‐dependent changes in the frequency response, the refractive index, and/or the absorption coefficient of the polymer. This article introduces nonlinear optical phenomena and the structural properties that enhance a material's nonlinear optical response. Second‐and third‐order nonlinear optical (NLO) phenomena are discussed, with a primary emphasis on harmonic generation, intensity‐dependent refractive index, and nonlinear, multiphoton, absorption. Macroscopic nonlinear phenomena are related to the molecular properties of the materials. Sum‐over‐states models are used to understand the fundamental molecular parameters affecting the nonlinear response, particularly π‐electron conjugation, bond length alternation, and donor–acceptor substitution. Measurement techniques used to characterize a material's nonlinear response are surveyed.