In the fluorescence spectra only morphine exhibits large red shifts of the maxima on increasing solvent polarity. In the phosphorescence spectra, phenol, anisole, and 3-methoxyphenol exhibit large red shifts of the maxima on going from nonpolar to polar solvents. For the latter, the results are interpreted in terms of charge-transfer-to-solvent (CTTS) transitions. For morphine, 2- and 4-methoxyphenol, the phosphorescence maxima occur at long wavelengths in both nonpolar and polar solvents, and this is interpreted in terms of CTTS and intramolecular charge transfer processes. The red-shift of the morphine fluorescence band on going to polar solvents is similarly interpreted as a combination of CTTS and intramolecular charge transfer transitions.