Solvent and substituent effects on the absorption spectra of Brooker's merocyanine (BM) are investigated using the threedimensional reference interaction site model self-consistent field method and time-dependent density functional theory. The π–π* excitation energies are computed for BM and its derivative 2,6-di-tert-butyl (di-t-Bu) BM. The behaviors of the computed excitation energies with increasing solvent polarity are in good agreement with those of the corresponding experimental measurements. In addition, analysis of the solute–solvent interaction energies and spatial distribution functions reveals that the effects of the solvent on the absorption spectra are reduced by the steric hindrance of the t-Bu groups. Furthermore, from the difference in the solute–solvent interaction energies of BM and di-t-Bu BM, it is shown that the effect of the t-Bu substituents on the absorption spectrum is greater in high-polarity solvents.