We report in this work the morphological, structural and hydrogen generation properties of V2O5 (VO) synthesized by a wet chemical method. We obtained morphologies of nanoplates and nanopillars by using sunflowers’ petals and the center of sunflower (disk florets) as biodegradable templates during the synthesis. A morphology of microbelt is obtained in absence of a biodegradable template in the synthesis. According to the X-ray patterns, the microbelts presented a pure orthorhombic phase, while the nanoplates and nanopillars had a mixture of monoclinic/orthorhombic phases. The monoclinic phase corresponded to VO2 and its content was below 3%. The performance of the three morphologies was evaluated for hydrogen generation under simulated solar light and obtained a maximum hydrogen generation rate of 65.5 μmol g−1 h−1 for the nanopillars. In general, the hydrogen generation decreased in the order: VO-nanopillars > VO-nanoplates > VO-microbelts. The morphology on nanopillars presented the highest hydrogen generation because it had the highest absorption of light as well as the highest content of defects (oxygen vacancies), which acted as electron trapping centers that delayed the electron-hole recombination. The presence of such defects in the VO with different morphologies was confirmed by photoluminescence measurements, since a red emission at 650 nm was observed. Hence, this study demonstrates that finding the optimum morphology for VO with the highest hydrogen production is relevant, since it can be employed to make nanocomposites with several heterojunctions, leading to higher hydrogen production rates.