Experiments have been performed to measure, in real time, the formation of AlO molecules from laser‐ablated Al atoms in oxygen gas and plasma environments. The Al atom plume is generated by focusing a KrF laser (4 J/cm2) on Al metal targets or polycrystalline Al2O3(alumina) ceramic. AlO molecule formation has been characterized by emission spectroscopy at 464.82 and 484.22 nm molecular bandheads. Time‐integrated and time‐resolved optical emissions have been measured of laser‐ablated Al atoms interacting with oxygen or argon neutral‐gas versus plasma backgrounds generated by a high‐voltage capacitive discharge. Results indicate that gas/plasma‐phase reactions occur between laser‐ablated Al atoms and oxygen. Optimal enhancement of AlO optical emission is measured in oxygen plasmas at about 200 mTorr fill pressure. ©1995 American Institute of Physics.