Abstract Detonation nanodiamonds (NDs) were studied by time‐of‐flight mass spectrometry (TOF MS). The formation of singly charged carbon clusters, C , with groups of clusters at n = 1–35, n ∼160–400 and clusters with n ∼8000 was observed. On applying either high laser energy or ultrasound, the position and intensity of the maxima change and a new group of clusters at n ∼70–80 is formed. High carbon clusters consist of an even number of carbons while the percentage of odd‐numbered clusters is quite low (≤5–10%). On increasing the laser energy, the maximum of ionization (at n ∼200 carbons) is shifted towards the lower m/z values. It is suggested that this is mainly due to the disaggregation of the original NDs. However, the partial destruction of NDs is also possible. The carbon clusters ( n ∼2–35) are partially hydrogenated and the average value of the hydrogenation was 10–30%. Trace impurities in NDs like Li, B, Fe, and others were detected at high laser energy. Several matrices for ionizing NDs were examined and NDs themselves can also be used as a matrix for the ionization of various organic compounds. When NDs were used as a matrix for gold nanoparticles, the formation of various gold carbides Au m C n was detected and their stoichiometry was determined. It was demonstrated that TOF MS can be used advantageously to analyze NDs, characterize their size distribution, aggregation, presence of trace impurities and surface chemistry. Copyright © 2009 John Wiley & Sons, Ltd.