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Novel additive technology of the Chemical Metallization of Photopolymer-based Structures (CMPS) is under active elaboration currently at the IAP RAS (Nizhny Novgorod). The use of this technology has made it possible to implement components of electron–optical and electrodynamic systems for high-power microwave vacuum tubes, such as a gyrotron and a relativistic Cherenkov maser, the design and experimental studies of which are described in this paper. Within the framework of the gyrotron developments, we carried out a simulation of the distribution of the heat load on the collector of high-power technological gyrotron taking into account secondary emission. The prospect of a significant reduction in the maximum power density of the deposited electron beam was shown. The experimental study of the gyrotron collector module manufactured using CMPS technology demonstrated high potential for its further implementation. Recent results of theoretical and experimental studies of a spatially extended Ka-band Cherenkov maser are presented. In this oscillator, the 2D-periodical slow-wave structure made by the proposed technology was applied and a narrow-band generation regime was observed with a sub-GW power level. The design and simulations of a novel selective electrodynamic system for a high-harmonic gyrotron with the planned application of the CMPS technology are discussed.