Laser Desorption Ionisation (LDI) and Matrix‐Assisted Laser Desorption Ionisation (MALDI) Time‐of‐Flight Mass Spectrometry (TOFMS) were used to study the pulsed laser ablation of aluminium nitride (AlN) nano powder. The formation of Alm+ (m = 1–3), Nn+ (n = 4, 5), AlNn+ (n = 1–5, 19, 21), AlmN+ (m = 2–3), Al3N2+, Al9Nn+ (n = 5, 7, 9, 11 and 15), Al11Nn+ (n = 4, 6, 10, 12, 19, 21, 23, and 25), and Al13Nn+ (n = 25, 31, 32, 33, 34, 35, and 36) clusters was detected in positive ion mode. Similarly, Alm– (m = 1–3), AlNn– (n = 1–3, 5), AlmN– (m = 2, 3), Al2Nn– (n = 2–4, 28, 30), Nn– (n = 2, 3), Al4N7–, Al8Nn– (n = 1–6), and Al13Nn– (n = 9, 18, 20, 22, 24, 26, 28, 33, 35, 37, 39, 41 and 43) clusters were observed in negative ion mode. The formation of the stoichiometric Al10N10 cluster was shown to be of low abundance. On the contrary, the laser ablation of nano‐AlN led mainly to the formation of nitrogen‐rich AlmNn clusters in both negative and positive ion mode. The stoichiometry of the AlmNn clusters was determined via isotopic envelope analysis and computer modelling. Copyright © 2011 John Wiley & Sons, Ltd.