The pore structure of volcanic fractured oil reservoirs is complicated, and the traditional gas displacement and waterflooding are not ideal. In this paper, the pore structure characteristics of volcanic rock were analyzed. Then, the diffusion procedure of CO2 and natural gas in saturated oil porous media was analyzed by pressure drop method. Finally, huff-n-puff experiments of CO2 and natural gas were conducted to analyze factors on the recovery factor (RF), and the oil mobilization pattern was quantitatively characterized. By huff-n-puff, we mean injecting gas from one end and then soaking it for a period of time before producing oil, utilizing pressure-driven and physicochemical reactions to affect the oil. The results show that the pore size distribution range is large. The diffusion of CO2 and natural gas can be divided into three stages: rapid diffusion, slow diffusion and equilibrium, and the diffusion coefficient of CO2 is 10 times that of natural gas under same condition. Compared with vertical fractures and horizontal fractures, reticulate fractures have more influence on gas diffusion coefficient. After 6 cycles, the RF of CO2 is 15% higher than that of natural gas, and the contribution of the first 4 cycles to the RF is 91.38%. In addition, CO2 huff-n-puff primarily mobilizes oil in medium (0.1 μm < r < 1 μm) and large (r > 1 μm) pores. These research results can provide a good theoretical guidance for the efficient development of VFOR and CO2 sequestration.