Laser flash photolysis, phosphorescence and density functional calculations were used to characterize the triplet excited states of phenylethanol derivatives 1, 2, 3 and 4. In acetonitrile, the triplet excited states of these alcohols were formed with rate constants on the order of ~107 s–1 and decayed with rate constants between 105 and 106 s–1. The energies of these triplet excited states were between 80 and 83 kcal/mol. Furthermore, 3 can be used as a triplet sensitizer for alkyl azides to form triplet nitrene intermediates. Copyright © 2011 John Wiley & Sons, Ltd.