Recently, low-dimensional structures in the form of bulk crystals and nanoflakes have received considerable interest due to their 2D unique functionality and promising applications in electronics, photonics, sensing devices and photovoltaic solar cells. As a result, remarkable efforts and modifications have been made for the synthesis process of crystalline material by the vapor transport technique. Here, an alternative concept of NbSe2 crystal growth by the chemical vapor transport (CVT) technique using bromine as a vapor transport agent is presented and subsequently analyzed by X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS) spectroscopy. X-ray powder diffraction analysis revealed hexagonal 2H-NbSe2 and 4H-NbSe2 phases, and characteristic Raman and XPS spectra typical for crystalline NbSe2 were obtained. The environmental sensitivity of the grown crystals is manifested by luminescence attributed to oxidized Nb at the samples’ surface.