A deep trench isolation structure of a high-voltage device and a method of forming thereof. An epitaxial layer with a second type conductivity is formed on a semiconductor silicon substrate with a first type conductivity. A deep trench passes through the epitaxial layer. An ion diffusion region with the first type conductivity is formed in the epitaxial layer and surrounds the sidewall and bottom of the deep trench. An undoped polysilicon layer fills the deep trench.