In this paper, argon was used in radio frequency (13.56 MHz) dielectric barrier discharge (rf-DBD) at atmospheric pressure. The IV curve was recorded after gas breakdown, and discharge photos were captured by ICCD camera. Discharges of α mode and γ mode were observed based on IV curve and ICCD photos. As the existence of negative glow in γ mode, the luminescence intensity of different position of the discharge gap was analyzed. It was found that in the α mode, the electron avalanche occurs from negative to positive and negative glow appeared after the discharge changed into γ mode. In every half cycle, the peak position of negative glow is 13 ± 1 ns later than that of electron avalanche on cathode surface.