A review is presented describing our recent work to correlate the first hyperpolarizability, β, of organic materials with the molecular parameter bond length alternation (BLA). Donor-acceptor polyenes displaying a wide BLA range were synthesized. For a particular chromophore, BLA was fine-tuned by varying solvent polarity. The degree of BLA was analyzed by X-ray diffraction, 1H-NMR and electronic absorption spectroscopy. Non-resonant, solvent-dependent, electric field induced second harmonic generation (EFISH) Measurements were performed to probe the variation in the second-order nonlinearity as a function of ground-state polarization. The resulting trend, which is fully consistent with theoretical predictions, identified chromophores possessing optimized positive and negative hyperpolarizabilities. An optimized chromophore was incorporated in a polymer matrix and poled. The resulting electro-optic coefficient was found to be significantly enhanced relative to the longer chromophore Disperse Red 1.