In this work, we studied the influence of technological parameters of plasma chemical etching of silicon on silicon etching rate, photoresist etching rate, etching selectivity of silicon in relation to a photoresist, and sidewall angle of etched structures. It was found that the silicon etching rate increases with raising percentage of SF6 in the gas mixture (25%–50%), pressure (1–2.5 Pa), high-frequency (HF) power (1000–2000 W), and bias voltage module (15–75 V) and decreases with a raising total flow rate of the gas mixture (5–35 SCCM) due to the increasing passivation efficiency of the sample surface. The etching selectivity increases with a raising percentage of SF6 and pressure and decreases with the raising total gas flow rate, HF power, and bias voltage module due to different influences of technological parameters on the photoresist etching rate. In addition, based on the obtained results, a common regularity between the sidewall angle and the optical emission spectra was revealed. The method of in situ diagnostics was proposed, namely, controlling the sidewall angle by a ratio of emission intensities of a carbon line (517.1 nm) to a fluorine line (685.8 and 703.9 nm) designated as parameter X. It was found that the sidewall angle of etched structures takes certain values depending on the value of the X parameter. The ranges of X values at which the sidewall angle is acute, right, and obtuse were estimated. So, at values of X from ≈0.15 to ≈0.35, an acute angle (from 81° ± 0.5° to 89° ± 0.5°) is obtained; at X from ≈0.35 to ≈0.42, a right angle is obtained (90° ± 0.5°); and at X from ≈0.42 to ≈0.75, the values of the sidewall angle are in the range from 91° ± 0.5° to 94° ± 0.5°, no matter which technological parameters were set. Experiments were conducted for etching windows with linear dimensions from 0.5 × 20 to 2 × 20 mm.