The photocatalytic decomposition of ethylene was performed under UV-LED irradiation in the presence of nanocrystalline TiO2 (anatase, 15 nm) supported on porous nickel foam. The process was conducted in a high-temperature chamber with regulated temperature from ambient to 125 °C, under a flow of reacted gas (ethylene in synthetic air, 50 ppm, flow rate of 20 mL/min), with simultaneous FTIR measurements of the sample surface. Ethylene was decomposed with a higher efficiency at elevated temperatures, with a maximum of 28% at 100–125 °C. The nickel foam used as support for TiO2 enhanced ethylene decomposition at a temperature of 50 °C. However, at 50 °C, the stability of ethylene decomposition was not maintained in the following reaction run, but it was at 100 °C. Photocatalytic measurements conducted in the presence of certain radical scavengers indicated that a higher efficiency of ethylene decomposition was obtained due to the improved separation of charge carriers and the increased formation of superoxide anionic radicals, which were formed at the interface of the thermally activated nickel foam and TiO2.