In this work we examine the room temperature photoluminescence, Raman and low temperature photoluminescence properties of CuAlO2 prepared using different precursors. At room temperatures the luminescence associated with bulk CuAlO2 occurs at 355 nm and is associated with strong resonant Raman effects. At low temperatures we find that the UV emission is dominated by strong electron– phonon coupling leading to a Franck–Condon type emission band. A second strongly phonon coupled band is also observed in the blue spectral region. In addition we also show that at low temperatures the luminescent properties of CuAlO2 are meta-stable, with anomalous temperature dependence. The possible origins of the blue band, the meta-stability and anomalous temperature dependence are discussed.