The technology of aerobic granular sludge (AGS) seems prospective in wastewater bio-treatment. The characteristics as well as compactness and structure of AGS have been proved to significantly affect the effectiveness of thus far deployed methods for sewage sludge processing, including anaerobic digestion (AD). Therefore, it is deemed necessary to extend knowledge on the possibilities of efficient AGS management and to seek viable technological solutions for methane fermentation of sludge of this type, including by means of using the pre-treatment step. Little is known about the pre-treatment method with solidified carbon dioxide (SCO2), which can be recovered in processes of biogas upgrading and enrichment, leading to biomethane production. This study aimed to determine the impact of AGS pre-treatment with SCO2 on the efficiency of its AD. An energy balance and a simplified economic analysis of the process were also carried out. It was found that an increasing dose of SCO2 applied in the pre-treatment increased the concentrations of COD, N-NH4+, and P-PO43− in the supernatant in the range of the SCO2/AGS volume ratios from 0.0 to 0.3. No statistically significant differences were noted above the latter value. The highest unit yields of biogas and methane production, reaching 476 ± 20 cm3/gVS and 341 ± 13 cm3/gVS, respectively, were obtained in the variant with the SCO2/AGS ratio of 0.3. This experimental variant also produced the highest positive net energy gain, reaching 1047.85 ± 20 kWh/ton total solids (TS). The use of the higher than 0.3 SCO2 doses was proved to significantly reduce the pH of AGS (below 6.5), thereby directly diminishing the percentage of methanogenic bacteria in the anaerobic bacterial community, which in turn contributed to a reduced CH4 fraction in the biogas.