We present a time-dependent quantum-chemical analysis on merocyanine aggregates to understand the insight of the intermolecular interactions and to find the relationship between structural and collective nonlinear optical properties. The first hyperpolarizabilities are evaluated for monomer and aggregates of a series of zwitterionic merocyanine dyes, whose synthesis and formation of H and J type aggregates in solvents are reported recently in the literature (J. Am. Chem. Soc. 2002, 124, 943 1). The molecular geometries are obtained via B3LYP/6-31G** (hybrid density-functional theory) optimization including PCM approach, while the dynamic NLO properties are calculated with the TD-DFT/SOS and ZINDO/CV method including solvent effects. It has been observed that the first hyperpolarizability changes tremendously as monomers undergo aggregation, and the magnitude of first hyperpolarizabilities highly depends on the nature of the aggregates. It is found that solvents play a remarkable role on the structure and first hyperpolarizabilities of merocyanine monomers and aggregates. Changing the solvent from low to high dielectric causes not only an increase in magnitude of beta but also a change in sign, therefore passing through zero at intermediate dielectric. The importance of our results on the design of electrooptic materials have been discussed.