Herein, we have reported the facile synthesis of pure and neodymium (Nd)-doped BaTiO3 powders via the hydrothermal method. The effects of Nd concentration (2–10 wt %) on the properties of the BaTiO3 powders were studied. Structural and morphological characteristics were realized using X-ray diffraction (XRD), scanning electronic microscopy (SEM), energy dispersive X-ray (EDS), and X-ray photoelectron spectroscopy (XPS). Fourier transform infrared (FT-IR), UV–visible, and photoluminescence (PL) spectroscopies were used for optical analyses. XRD results show that all powders crystallized under a cubic structure with an average crystallite size that was in the range of 35–47 nm. SEM micrographs revealed that the grains were spherical-shaped, with an average size found in the range of 232–390 nm. The EDS analysis detected the presence of Ba, Ti, O, and Nd elements in the elaborate materials. XPS data confirms the introduction of Nd3+ in the BaTiO3 and the amphoteric substitution of Nd3+ in the Ba and Ti sites at 6 and 10 wt%. FT-IR spectra indicate the presence of the Ti–O vibration bonds. UV–visible optical spectra illustrate the enhancement of absorbance with Nd doping. PL spectra exhibit ultraviolet, blue, green, and orange emissions in the samples.