Acidified CO2 fracturing is a viable method for increasing production in deep, tight sandstone reservoirs. However, the potential mechanism of changes in pore structure and mechanical properties of sandstone under acidified CO2 supercritical composite is not clear. Understanding this mechanism is important for the study of crack initiation and extension in tight sandstone reservoirs. This study utilizes sandstone samples from the Xujiahe Formation reservoir in Rongchang District as experimental specimens. The primary focus is to analyze the changes in pore structure and mechanical properties of these samples after acidification–supercritical CO2 composite action. Nuclear magnetic resonance (NMR) and uniaxial compression tests are employed as the main investigative techniques. The results show that there was a physicochemical synergy between the acidification–supercritical CO2 composite effect; the crack initial stress, damage stress, and peak stress of the sandstone after 16 MPa supercritical CO2 acidification treatment were reduced by 20%, 49.5%, and 49.8%, respectively; the crack volumetric strain accelerated and the sandstone evolved from brittle to ductile damage; and the larger pore space and microcracks of the sandstone increased significantly after the treatment, which can be attributed to the gradual dissolution of intergranular cement leading to the formation of new pores connected to the existing pore network. The change mechanism of sandstone after acidification–supercritical CO2 compound treatment is also proposed.