Barium titanate photocatalysts were synthesized via a sol–gel method involving a unique, cost-effective calcination technique that includes rapid heating and short exposure. The samples were characterized by X-ray diffractometry, scanning electron microscopy, diffuse reflectance spectroscopy, photoluminescence spectroscopy, infrared spectroscopy, and nitrogen adsorption–desorption measurements. The photooxidation activity and stability of the samples were evaluated by the degradation of phenol, oxalic acid, and chlorophenol. Their photoreduction activity was also investigated by the photocatalytic conversion of CO2 to CO. In both cases, UV irradiation was applied to activate the catalysts. As references, commercially available cubic and tetragonal barium titanates were used, with the addition of benchmark P25 TiO2 in some cases. Increasing the calcination temperature resulted in increased primary crystallite sizes, decreased specific surface areas, and slightly redshifted band gaps. On the one hand, the overall photooxidation activity of the samples for pollutant degradation was rather low, possibly due to their unfavorable valence band maximum position. On the other hand, our samples displayed significantly superior photoreduction activity, surpassing that of all the references, including P25 TiO2. The high photoactivity was mainly attributed to the specific surface areas that changed per the efficiency of the samples. Last, the cost comparison calculations showed that applying our calcination technique is 29.5% more cost-efficient than conventional calcination, and the same amount of energy is sufficient for preparing even a 1.4 times higher amount of barium titanite.