Due to the excellent properties, C4F7N/CO2 mixture is the most concerned eco-friendly SF6 alternative gas. For a better understanding of the surface discharge characteristics, the surface discharge pattern of C4F7N/CO2 mixture under negative impulse voltages is investigated in this work. The morphology of the surface discharge is obtained by an optical method and a dust figure method. The structure of the surface discharge is established, which from the outside to the inside consists of electron cloud, streamer, streamer stem, and leader. The propagation pattern of the surface discharge in C4F7N/CO2 mixture under negative impulse follows the stepwise expansion pattern. The structure of the surface discharge in C4F7N/CO2 mixtures with different ratios and SF6 has no obvious difference, and the propagation pattern is also the same. The results of this work can help to better understand the surface discharge phenomenon and the insulation characteristics of C4F7N/CO2 mixture.