Abstract The formation and growth of hydrogen bubbles on a Si(1 0 0) surface during its anisotropic etching in aqueous KOH has been investigated. Quantitative data on bubble size, lifetime and density on the etching surface was obtained and their dependence on KOH concentration, applied potential and temperature were measured. In situ FTIR measurements demonstrated a strong dependence of bubble attachment on surface termination and hence on the hydrophilicity of the Si(1 0 0) surface during etching. The formation of surface defects and the geometry of bubble imprints have been directly characterised with scanning probe microscopy. The analysis of hillock formation and statistical considerations show that the adhesion of hydrogen bubbles during anisotropic etching of silicon is a source of surface roughness and pyramid formation.