The past decades have witnessed the development of new materials with large nonlinear optical properties, which have made them attractive candidats for a broad spectrum of breakthrough applications in the electro-optic and photonic fields (e.g., telecommunication and computing). A deeper understanding of the relationship between, on the one hand, the chemical structure and, on the other hand, the electronic and (linear and nonlinear) optical properties has proven useful for the rational design of new efficient materials. Reaching such an understanding has attracted major interest in the scientific community worldwide in both academia and industry. Therefore, the development of new efficient NLO chromophores and materials along with commercial devices of high quality is helped via the establishment of multidisciplinary research teams combining: (i) the theoretical modeling using quantum-chemical computational calculations; (ii) the organic synthesis; (iii) the optical characterization; and (iv) the device fabrication. In this dissertation, quantum-chemistry is used to evaluate the second- and third-order NLO properties of series of new chromophores and take advantage of a feedback loop with the experimental team to understand the structure-property relationships.