TiO₂-supported clinoptilolite (TiO₂/CP) was synthesized in the presence of F⁻ ions. Various characterizations demonstrated that the particle size of loaded TiO₂ increased linearly with an increase in the temperature and concentration of F⁻ ions. In particular, the additive F⁻ ions were favored to produce the mutually independent co-exposed {001} and {101} facets of loaded TiO₂, while TiO₂/CPs synthesized in the absence of F⁻ ions were dominated by the thermodynamically stable {101} facet. As photocatalysts for the removal of crystal violet or methyl orange dyes under UV-irradiation in aqueous solutions, TiO₂/CPs (ACP6) synthesized in the presence of F⁻ ions significantly improved the degradation efficiency, as compared to ACP3 obtained in the absence of F⁻ ions. These results elucidated that the highly energetic {001} exposed facet, large particle size and fine dispersion of loaded TiO₂ in TiO₂/CP accounts for its best photocatalytic performance. The effected mechanism of operational parameters on the degradation performances is proposed.