We introduce an approach toward the synthesis of micro- and nanostructures under nonequilibrium microwave discharges within metal–dielectric powder mixtures induced by powerful microwave gyrotron radiation. A new plasma-chemical reactor capable of sustaining a discharge regime with an afterglow phase of an order of magnitude longer than the gyrotron pulse duration was constructed for these experiments. In the nonequilibrium conditions of such a discharge, plasma-induced exothermic chemical reactions leading to the synthesis of various compounds were initiated. The synthesized structures were deposited on the reactor walls and on the impurity particles within the reactor. This method was tested under gyrotron-initiated discharges within various metal–dielectric powder mixtures of titanium–boron, molybdenum–boron, titanium–silicon–boron, molybdenum–boron nitride, molybdenum–tungsten–boron nitride, and so on. Depending on the powder mixture composition, reactor atmosphere, and other parameters, micro- and nanosized particles of boron nitride, titanium diboride, molybdenum boride, titanium boride, molybdenum, and molybdenum oxide, were synthesized, detected, and analyzed.