Reactive ion etching (RIE) is a promising material removal method for processing membrane diffractive optical elements and fabrication of meter-scale aperture optical substrates because of its high-efficiency parallel processing and low surface damage. However, the non-uniformity of the etching rate in the existing RIE technology will obviously reduce the machining accuracy of diffractive elements, deteriorate the diffraction efficiency and weaken the surface convergence rate of optical substrates. In the etching process of the polyimide (PI) membrane, additional electrodes were introduced for the first time to achieve the modulation of the plasma sheath properties on the same spatial surface, thus changing the etch rate distribution. Using the additional electrode, a periodic profile structure similar to the additional electrode was successfully processed on the surface of a 200-mm diameter PI membrane substrate by a single etching iteration. By combining etching experiments with plasma discharge simulations, it is demonstrated that additional electrodes can affect the material removal distribution, and the reasons for this are analyzed and discussed. This work demonstrates the feasibility of etching rate distribution modulation based on additional electrodes, and lays a foundation for realizing tailored material removal distribution and improving etching uniformity in the future.