Thermal residual stress in diamond film deposited onto Mo substrate was simulated and analyzed comprehensively by using the finite element method on condition that the substrate’s plasticity was considered. The contour plots of the stresses were described. Moreover, the effect of the film’s thickness on thermal residual stress was investigated. The results show that every stress component in the film has the remarkable stress concentration at the intersection of the interface and the side of the film. The location of maximum tensile principal stress in the film is at the upward face or side face of the film or the interface. The magnitude of maximum tensile principal stress increases when the film becomes thicker. These conclusions are useful to the proper choice of the film’s thickness and the effective control of the stresses during preparation of diamond film.