Chemical vapor deposition (CVD) diamond coatings were deposited on milling cutter substrate using a hollow substrate holder. The substrate is WC–Co cemented carbide contained 6% of cobalt concentration. Structures and stress state of diamond films were analyzed by scanning electron microscopy (SEM) and Raman spectroscopy. It was found that the diamond coating is of the same quality at the same cutting tool deposited on a hollow substrate holder. Diamond (sp3) bonds are better developed with substrate temperature of ~760°C. A higher or lower substrate temperature could lead to a higher non-diamond carbon content in the films. A higher substrate temperature could lead to a higher thermal stress. The compressive stress increases when the substrate temperature is higher or lower than 760°C. The concentration of amorphous phase in the coatings is low with CH4 concentration of 1.0% and 1.5%. A higher non-diamond carbon content and defects in the diamond coatings increase with the increase of CH4 concentration, which leads to the compressive stress value does not increase significantly under a high CH4 concentration.