Titanium(IV) oxide is commonly used in photocatalysis. However, it has some drawbacks, e.g., a high rate of electron-hole recombination and a wide bandgap. In here, the surface of anodic titanium(IV) oxide (ATO) was modified with metal nanoparticles (gold, silver, and copper) in order to enhance its photoelectrochemical (PEC) and photocatalytic (PC) properties. SEM analysis revealed that Au, Ag, and Cu nanoparticles obtained on an ATO surface by chemical methods had an average diameter of 50 ± 10 nm, 30 ± 6 nm, and 25 ± 3 nm, respectively. Enhancement of photoelectrochemical water-splitting current efficiency in the wavelength range of 300–400 nm was observed due to the occurrence of the Schottky barriers. However, the nanoparticles had no effect on the current efficiency in the range of 400–600 nm which meant that the surface plasmon resonance (SPR) effect was not observed. A rate of methyl red photodecomposition was improved after the modification of the ATO surface. The best results were obtained for ATO decorated with gold nanoparticles.