The composition of the gaseous phase during pyrolytic laser-induced chemical vapour deposition (LCVD) of aluminium from trimethylaluminium (TMA) was determined. The analysis was carried out in situ by means of a quadrupole mass spectrometer (QMS) in a closed reaction cell. The decomposition of the aluminium alkyl was induced by a copper bromide vapour laser on the surface of (111) silicon monocrystalline wafer at 0.22 GW m−2 average power density, 120 μm s−1 scanning speed and 100 Pa (1 mbar) partial pressure of TMA. The detected gaseous products of the pyrolysis of TMA were ethane, ethylene, methane and hydrogen. The presence of ethane and ethylene was probably due to the unconventional way of decomposition caused by pulsed laser irradiation. The mass peak dynamics of the created pyrolytic products at m/e = 28, 16 and 2 indicated significant production of ethane + ethylene, methane and hydrogen in the ratio 1:5:1.75.