A method of forming a contact structure is provided. A silicon-containing substrate is provided with a composite dielectric layer formed thereon. An opening penetrates through the composite dielectric layer and exposes a portion of the source/drain region. A titanium nitride layer is formed in the opening, and the titanium nitride layer is in contact with the exposed portion of the source/drain region. The titanium nitride layer is annealed, so that the bottom portion of the titanium nitride layer is partially transformed into a titanium silicide layer. A conductive layer is formed to fill up the opening.