Nanoporous tantalum nitride (Ta3N5) is a promising visible-light-driven photoanode for photoelectrochemical (PEC) water splitting with a narrow band gap of approximately 2.0 eV. It can utilize a large portion of the solar spectrum up to 600 nm to improve the activity of photooxidation reactions because of enhanced light scattering and an overall increase of the surface area with high light absorption and carrier collection. Herein, we synthesized a new n-type nanoporous tantalum nitride film on Ta foil by electrochemical anodization with a fluorinated electrolyte. Post-annealing in a nitrogen/ammonia mixture gas environment then transformed amorphous TaOx to crystalline Ta3N5. Effects of annealing temperature on the microstructure, optical properties, and PEC properties of samples were then investigated under changeable stoichiometry of Ta and N elements in the Ta-based nitride film. Results showed that the film annealed at 1000 °C showed high crystallinity, high visible light absorption, and a highly conductive interlayer between the substrates, resulting in the highest photocurrent density (JSC) of ∼0.25 mA cm-2 at 1.23 VRHE in PEC water splitting. In addition, depending on the annealing temperature, it is possible to engineer band alignment in the nanoporous Ta3N5 layer, allowing a beneficial charge transfer process.