A direct current (dc) glow discharge—surface interaction process for in situ substrate surface pretreatment, for the promotion of diamond growth on mirror polished Si(100) is reported. A key step of the pretreatment is a generation of a stable dc-glow discharge between a grounded substrate and a positively biased electrode using a CH4/H2 gas mixture. During this stage, no additional gas phase activation by a hot filament is carried out. For subsequent diamond deposition, the dc-glow discharge is switched off and the standard hot filament CVD growth conditions are applied. The nature of the deposits formed by the dc-glow discharge process and after standard diamond deposition conditions, are investigated by Raman spectroscopy and high resolution scanning electron microscopy. It is found that the properties of the films, deposited following the dc-glow discharge pretreatment, strongly depend on the pretreatment conditions: methane concentration, substrate temperature, and pretreatment time. It is suggested that the nature of the diamond precursor formed during the dc-glow discharge pretreatment is similar to that one observed after bias enhanced nucleation process. © 1998 American Institute of Physics.