Dioxins are extremely toxic, and it is difficult to treat them with the conventional method. When irradiated by light, photocatalysts generate strong oxidative potential and decomposes almost all organic substances containing dioxins to water, carbon dioxide and others. Silica-gel has high adsorptive activity as well as large surface area, and it is transparent to ultraviolet light. Photocatalytic silica-gel was prepared by a dip coating method using TiO2 sol obtained by hydrolyzing titanium tetraisopropoxide on silica-gel bead (about 3mm in diameter) and heat-treated at 550 degrees C. Since the surface area of the photocatalytic silica-gel is 300m(2)/g, the reaction area is large and allows the highly efficient decomposition of harmful organic substances, unpleasant odors and colored matters contained in waste water. The photocatalytic apparatus for decomposition of dioxins in emission gas from waste incinerators is composed of the catalyst layer consisting of 95dm(3) photocatalytic silica-gel and 16 units of UV lamp. The photocatalytic apparatus was connected to the bypass line led from the outlet duct of cyclone, and the concentration of dioxins in the exhaust gas was measured. Decomposition test of dioxins in scrubber water was also performed using a photocatalytic apparatus with 150g photocatalytic silica-gel and 8 units of UV lamp. After 0.5 dm(3) of scrubber water containing dioxins was circulated in the photocatalytic apparatus for 1, 2 and 24 hour, each concentration of dioxins in the water was measured. As a result, the removal efficiency over 99% of dioxins in emission gas and scrubber water from waste incinerators has been obtained.