The features of cumene dehydrogenation to α-methylstyrene on unique porous ceramic catalytic converters having the composition [Re,W]/γ-Al2O3(K,Ce)/α-Al2O3 and [Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3, obtained using self-propagating high-temperature synthesis and the sol–gel method, have been studied. It has been established that at an optimum temperature of 625°C, the rhenium–tungsten-containing system has approximately 1.5 times higher catalytic activity than the iron–chromium system. On the Re–W-containing catalytic converter at the optimum temperature, the cumene conversion is ~71 mol %, the α-methylstyrene yield is ~77 mol % of theoretical, and the α-methylstyrene content in the products is ~35 mol %, with productivity for the desired product being ~7.4 g/(h gact.comp.). The degree of catalyst coking for 6 h of the experiment did not exceed 5 wt %.