Terahertz (THz) spectroscopy is an emerging technology with promising applications in imaging, homeland security, and material detection and quantification. Frequencies in the THz region can be generated by optical rectification of ultrafast near-infrared laser pulses in the presence of a nonlinear optical (NLO) materials such as organic crystals. Non-centrosymmetric organic THz generating crystals such as DAST, HMQ-TMS, and OH1 have received special attention due to the strong generated fields on the order of MV/cm. The cation of these organic salts is designed by connecting electron-donating with electron-accepting groups via a highly planar aromatic system. To improve the performance of organic crystals for THz generation, the molecular hyperpolarizability (β) can be optimized by introducing modifications in the architecture of these push-pull chromophores. However, the large dipole moments associated with molecules that have a large β promote the formation of NLO inactive centrosymmetric molecular alignments in the crystal state. This dissertation provides important insights into the design of new push-pull chromophores that feature a) higher β values compared with state-of-the-art organic crystals, and b) non-centrosymmetric molecular packing in the crystalline state. The first strategy presented on this dissertation relates to the introduction of a triple bond instead of a double bond in the cation of DAST to improve the β parameter. The newly designed 4DEP core was combined with different anions to promote non-centrosymmetric molecular packing with almost ideal arrangements for THz generation. However, large single crystals were difficult to obtain and high THz generation was not achieved. The second strategy presented in this dissertation raises the value of β by extending the π-conjugation length in different cations with dimethylamino and methoxy electron-donating groups. A new molecular cation, 6MNEP, was found to have large β value combined with ideal non-centrosymmetric molecular packing. Combining these two factors, a ~ 75% higher performance for THz generation is expected for 6MNEP compared with DAST. Currently, we are testing different crystallization techniques to grow large single crystals of 6MNEP. In addition to the strategies developed to increase the β parameter value, we also introduce a new molecular modification to induce non-centrosymmetric packing in organic salt THz generating crystals. This is achieved by substituting a methyl by an ethyl group in the quaternary nitrogen of hydrogen-bonded crystals. We showed the applicability of this method for changing molecular packing in the crystal state from centrosymmetric to non-centrosymmetric in two different molecular cations. We also demonstrated the generation of strong THz fields in the novel NLO crystal EHPSI-4NBS.