TiO₂ nanotube (TNT) supported Rh and Ru nanoparticle catalysts were prepared via impregnation-photoreducing procedure and characterized with various methods. Their catalytic performances in hydroformylation were evaluated by using vinyl acetate and cyclohexene as substrates. The results indicate that the presence of Ru in the catalysts can enhance the catalytic activity of catalysts for the hydroformylation of vinyl acetate, but do not play the same role in the hydroformylation of cyclohexene; the sequence of loading metal has a significant effect on the catalytic performances of the title catalysts. Additionally, it is found that Ru/TNTs shows catalytic activity for the hydroformylation of vinyl acetate though it does not for the hydroformylation of cyclohexene.