Cerium-doped titania nanoflowers are obtained by hydrothermal synthesis, with different amounts of cerium (0.3, 0.5, and 1.0 at%). Both undoped nanoflowers (TNF) and Ce-doped TNF (Cex) are tested as photocatalysts in the degradation of the target pollutant (metronidazole) under simulated solar light. The samples are rutile polymorphs with high crystallinity and present a nanoflower-like morphology of about 1 µm in diameter and are made up of nanoscale petals (in the range of 100–300 nm). EDX spectroscopy was coupled with SEM and performed on the Ce-doped samples to determine the elemental composition of the catalysts and the Ce distribution in each sample. Optical and electronic spectroscopies reveal that Ce loading narrows the band gap from 3.0 to 2.8 eV, extending light absorption into the visible range of the spectrum and thus enhancing the photocatalytic activity. The best sample, Ce1, achieved 67% degradation of metronidazole after 360 min under solar irradiation at pH 4, compared to bare TNF, which reached 35%. Reusability tests confirm the chemical stability and photocatalytic efficiency of Ce1 over three cycles, and free-radical trapping experiments confirmed ·O₂⁻ and ·OH as major active species in metronidazole degradation. This study highlights the synergistic impact of morphology and doping on solar-driven organic pollutant degradation.