Two-dimensional (2D) materials provide a platform to exploit the novel physical properties of functional nanodevices. Here, we report on the formation of a new 2D layered material, a well-ordered monolayer TiTe2, on a Au(111) surface by molecular beam epitaxy (MBE). Low-energy electron diffraction (LEED) measurements of the samples indicate that theTiTe2 film forms (√3 ×√7) superlattice with respect to the Au(111) substrate, which has three different orientations. Scan-ning tunneling microscopy (STM) measurements clearly show three ordered domains consistent with the LEED pattes. Density functional theory (DFT) calculations further confirm the formation of 2H-TiTe2 monolayer on the Au(111) surface with Te as buffer layer. The fabrication of this 2D layered heterostructure expands 2D material database, which may bring new physical properties for future applications.