The dissociation degrees of N2 and O2 are examined in a nitrogen–oxygen mixed microwave discharge plasma in a cylindrical quartz tube of 26 mm inner diameter with a discharge pressure of 0.5–1.0 Torr and a microwave power of 600 W by the actinometry method. We measured the electron temperature and density with a Langmuir double probe, while the vibrational and rotational temperatures of the first and second positive bands of N2 were measured by optical emission spectroscopy. Even when the line intensity of atomic nitrogen was weak and partly coincided with the high-intensity band spectrum of the first positive system due to its small dissociation degree, the actinometry method was found to be feasible when the first positive band spectrum, calculated as a function of the rotational and vibrational temperatures, was subtracted from that observed experimentally. It was found that the dissociation degrees of both N2 and O2 increase with the molar ratio of nitrogen in the mixed N2–O2 discharge gas for the same total discharge pressure. The experimental results are discussed by comparison with a simple numerical model based on chemical kinetics in the plasma. It was found that the dissociation of oxygen molecules is enhanced by the collision with excited nitrogen molecules, particularly those with metastable states, whereas that of nitrogen is suppressed by an admixture of oxygen molecules due to the chemical quenching processes of nitrogen atoms.