Polychlorinated dibenzofurans (PCDFs) are persistent toxic compounds that are ubiquitous in the environment. Nanocomposites of titanium(IV) oxide-vanadium(III) oxide (${\mathrm{Ti}}_3{\mathrm{V}}_2{\mathrm{O}}_7$) and titanium(IV) oxide-silicon dioxide (${\mathrm{Ti}}_2{\mathrm{Si}}_7{\mathrm{O}}_{30}$) were prepared and spectroscopically analyzed as potential decontaminants for dioxin-like materials. The analysis confirmed a homogeneous morphology with nanoscale particle size. The Ti-Si sample was found to have a high surface area compared to the Ti-V composite. Vanadium(III) oxide (V₂O₅) and silicon dioxide (SiO₂) were chosen as materials for the formation of heterogeneous compounds with titanium(IV) oxide (TiO₂) because they possess a suitable band alignment with TiO_2, thus forming effective photocatalysts. This study evaluated the photodegradation of 2,3,7,8-tetrachlorodibenzo-furan (TCDF) in the presence of Ti-Si and Ti-V oxide composites, which was tested using high- (254 nm) and midenergy (302 nm) UV irradiation sources. While Ti-Si showed success in the photodegradation of 2,3,7,8-TCDF dissolved in a (1:1) methanol–tetrahydrofuran (MeOH-THF) solution, the Ti-V composite proved to be a powerful material in adsorbing TCDF with a high capacity immediately upon mixing. Ti-Si oxide was found to decompose TCDF under the two irradiation sources with 98–99% degradation occurring after 70 min. The use of 254 nm as an irradiation source in the presence of Ti-Si was 4.3 times faster than the analogue reaction irradiated without a catalyst. Byproducts of the degradation were evaluated using gas chromatography–mass spectrometry (GC–MS), resulting in a lower chlorinated congener and less toxicity, as the main degradation product.