A combination of strategies for optimizing the molecular hyperpolarizability have been employed in the design of the molecules reported here: an aromatic moiety is linked to a planar-fixed polyene chain. The synthesis and nonlinear optical (NLO) characterization (absorption and electric-field-induced second harmonic generation) of the materials are described and their NLO properties compared-favorably-with those of 4'-dimethylamino-4-nitrostilbene, the prototypical organic material for electrooptic devices based on poled polymers.