We studied on the thermal annealing effect on the residual stress and the mechanical properties in thin compressive stressed diamond-like carbon film on Si substrate. Annealing experiments were carried out with Rapid Thermal Procedure system at 200–600 °C, and the stress change with annealing temperature was investigated by in-situ stress measurement system. The apparent stress reduction occurred with minimal structure changes. In order to measure the change of chemical structure of diamond-like carbon film by annealing, we used Raman spectrometer. The adhesion deterioration in interface has been detected as annealing temperature increased. In the compressive stressed DLC film, we observed the dramatic evolution of interface delamination at certain high temperature using in-situ heating stage built in Environment SEM. The quantitative change of adhesion affected by annealing process was also measured with scratch testing. For exploring the interface structure affected by the thermal annealing process at high temperature, the cross section of annealed film has been observed with HR TEM.