This study focused on mullite-based and forsterite-based ceramic bricks fired at 1000 °C from mixtures of fly ash (40 mass%) and kaolins or vermiculites (60 mass%). The structural, physical, and mechanical properties were characterized by X-ray powder diffraction, nitrogen physisorption, mercury porosimetry, thermogravimetry, and compressive strength. In the development of green-material-derived photocatalysts, we evaluated fly ash ceramic bricks based on kaolins and vermiculites, which deserve deeper research. Alkali potassium in the mixtures positively influenced the reduction of the firing temperature, shrinkage, small porosity, and high compressive strength of ceramic bricks. The crystallization of mullite in fly ash was observed on exotherm maxima from 813 to 1025 °C. Muscovite/illite admixture in kaolins precursor of mullite-based ceramics reduced the crystallization temperature of mullite by up to 70 °C. Vermiculite–hydrobiotite–phlogopite in mixed layers of a raw vermiculite precursor of forsterite-based ceramics controlled the formation of enstatite and forsterite in the temperature range from 736 ± 6 °C to 827 ± 6 °C. Mullite- and forsterite-based ceramic bricks were also investigated for photocatalytic hydrogen production. The photocatalytic generation of hydrogen in the presence of mullite-based ceramic bricks was positively correlated with the percentages of Fe2O3 in the lattice of mullites and in the presence of forsterite-based ceramics with the presence of diopside. Mullite-based ceramic produced the highest yield of hydrogen (320 µmol/gcat after 4 h of irradiation) in the presence of mullite with the highest 10.4% substitution of Fe2O3 in the lattice. The forsterite-based ceramic produced the highest hydrogen yields (354 µmol/gcat after 4 h of irradiation) over more active diopside than forsterite.