Single crystals of the trirutile structure MgTa₂O₆ were grown via an optical floating zone method in an air atmosphere. The as-grown crystals were pale yellow and transparent and the natural cleavage plane formed during the crystal growth was determined by XRD2 to be along the c-axis direction. The variations in valence were investigated by XPS (X-ray photoelectron spectroscopy). The room-temperature axis-relative polarized Raman spectra of trirutile MgTa₂O₆ crystals were described. The order–disorder effect was detected via temperature-dependent Raman spectroscopy.