In an industrial inductively coupled plasma reactor dedicated to silicon etching in chlorine-based chemistry, the density of Cl2 molecules and the gas temperature are measured by means of laser absorption techniques, the density of SiClx (x ⩽ 2) radicals by broadband absorption spectroscopy, the density of SiCl4 and ions by mass spectrometry, and the total gas pressure with a capacitance gauge. These measurements permit us to estimate the mole fractions of Cl, SiCl4, and etch product radicals when etching a 200 mm diameter silicon wafer. The pure Cl2 plasma is operated in well prepared chamber wall coating with a thin film of SiOCl, AlF, CCl, or TiOCl. The impact of the chemical nature of the reactor wall’s coatings on these mole fractions is studied systematically. We show that the reactor wall coatings have a huge influence on the radicals densities, but this is not only from the difference on Cl–Cl recombination coefficient on different surfaces. During silicon etching, SiClx radicals sticking on the reactor walls are etched by Cl atoms and recycled into the plasma by forming volatile SiCl4. Hence, the loss of Cl atoms in etching the wall deposited silicon is at least as important as their wall recombination in controlling the Cl atoms density. Furthermore, because SiCl4 is produced at high rate by both the wafer and reactor walls, it is the predominant etching product in the gas phase. However, the percentage of redeposited silicon that can be recycled into the plasma depends on the amount of oxygen present in the plasma: O atoms produced by etching the quartz roof window fix Si on the reactor walls by forming a SiOCl deposit. Hence, the higher the O density is, the lower the SiCl4 density will be, because silicon is pumped by the reactor walls and the SiOCl layer formed is not isotropically etched by chlorine. As a result, in the same pure Cl2 plasma at 20 mTorr, the SiClx mole fraction can vary from 18% in a SiOCl-coated reactor, where the O density is the highest, to 62% in a carbon-coated reactor, where there is no O. In the latter case, most of the Cl mass injected in the reactor is stored in SiCl4 molecules, which results in a low silicon etch rate. In this condition, the Cl mass balance is verified within 10%, and from the silicon mass balance we concluded that SiClx radicals have a high surface loss probability. The impact of the reactor wall coating on the etching process is thus important, but the mechanisms by which the walls control the plasma chemistry is much more complicated than a simple control through recombination reaction of halogen atoms on these surfaces.