The structure, photophysical properties, and photochemistry of the adamantyl aryl ethers 1 in both methanol and cyclohexane have been examined. UV absorption spectra, 13C NMR chemical shifts, X-ray structures, and Gaussian calculations (B3LYP/6-31G(d)) indicate that these ethers adopt a 90° conformer in the ground state. In contrast, fluorescence spectra, excited singlet state lifetimes, and calculations (TDDFT) indicated a 0° conformer is preferred in the first excited singlet state S1. Irradiation in either solvent results in the formation of adamantane and the corresponding phenol as the major products, both derived from radical intermediates generated by homolytic cleavage of the ether bond. The 4-cyano substituted ether 1j was the only one to form the ion-derived product, 1-methoxyadamantane (16% yield), on irradiation in methanol. Rate constants of bond cleavage for these ethers from S1 were estimated by two different methods by comparison with the unreactive anisoles 2, but the effect of substituents was too small to determine structurereactivity correlations. The temperature dependence of the quantum yields of the fluorescence of the unsub stituted, 4-methoxy and 4-cyano derivatives of 1 and 2 were also determined. These results indicated that the activated process for 1 was mainly bond cleavage for the 4-cyano substrate whereas for 2, it was internal conversion and intersystem crossing. Key words: aryl ether photochemistry, fluorescence, excited-state rate constants, excited-state temperature effects.