Abstract The formation of thin films of transition metal silicides is an important step in the manufacture of advanced semiconductor devices, particularly in VLSI technology. It is shown how chemical vapour deposition (CVD) of appropriate volatile molecular compounds containing silicon-metal bonds can lead to silicide film formation on a variety of substrates. Thus pyrolysis of H 3 SiCo( CO) 4, H 3 SiM( CO) 5 ( M= Mn, Re) and ( H 3 Si) 2 Fe( CO) 4 in a suitable flow system at 670–770 K produces respectively CoSi, M 5Si 3+MSi x(x≌1.25) , and β-FeSi 2. Both homogeneous and heterogeneous mechanisms for the production of silicides are discussed, and it is shown that a series of steps can be postulated, each of which is consistent with the known chemistry of molecular silicon-metal compounds or silicides. It is further shown that the compositions of the solid products resulting from static pyrolysis of these Si-M precursors can be accommodated within a similar mechanistic pattern.