The development of two-dimensional (2D) semiconductors is limited by the lack of doping methods. We propose surface isovalent substitution as an efficient doping mechanism for 2D semiconductors by revealing the evolution of the structure and electronic properties of 2D Se/Te. Because of the different electronegativity of Se and Te, Se substitution for Te at the specific lattice sites introduces electric dipoles and leads to charge redistribution, which lowers the work function and tunes the Te films from p-type to n-type semiconductors. This differs from the gap enlargement of alloy films with random Se-Te substitutions. This doping method minimizes the change of lattice structure and surface roughness, which benefits structure stacking. Further increasing the Se content leads to the formation of two types of 2D semiconducting Se polymorphs.