AlN epilayers with high optical qualities have been obtained by metalorganic chemical vapor deposition on sapphire substrates. Deep UV picosecond time-resolved photoluminescence (PL) spectroscopy has been employed to study the optical transitions in AlN epilayers. Two PL emission lines associated with the donor bound exciton (D0X, or I2) and free exciton (FX) transitions have been observed, from which the binding energy of the donor bound excitons in AlN epilayers was determined to be around 16 meV. Time-resolved PL measurements revealed that the recombination lifetimes of the I2 and free exciton transitions in AlN epilayers were around 80 and 50 ps, respectively. The temperature dependencies of the free exciton radiative decay lifetime and emission intensity were investigated, from which a value of about 80 meV for the free exciton binding energy in AlN epilayer was deduced. This value is believed to be the largest free exciton binding energy ever reported in semiconductors, implying excitons in AlN are an extremely robust system that would survive well above room temperature. This together with other well-known physical properties of AlN may considerably expand future prospects for the application of III-nitride materials. © 2003 American Institute of Physics.