Anisotropic 2D layered material rhenium disulfide (ReS2) with high crystal quality and uniform monolayer thickness is synthesized by using tellurium-assisted epitaxial growth on mica substrate. Benefit from the lower eutectic temperature of rhenium-tellurium binary eutectic, ReS2 can grow from rhenium (melting point at 3180 °C) and sulfur precursors in the temperature range of 460–900 °C with high efficiency.