Studies on harnessing solidified carbon dioxide (SCO2) for municipal sewage sludge (MSS) pre-treatment have been conducted exclusively in batch reactors. This makes it difficult to accurately assess how long-term SCO2 treatment affects anaerobic digestion (AD) conditions and performance. The aim of our study was to evaluate the effect of long-term MSS pre-treatment with SCO2 on AD conditions, anaerobic bacterial community, and biogas composition and yields. The presented experiments are the first studies on the effect of pre-treatment with SCO2 on the efficiency of AD of MSS in continuous reactors. So far, the impact of the organic load rate (OLR) on the efficiency of MSS methane fermentation has not been assessed, which is also a novelty of the conducted research. The AD process was conducted in continuous-stirred, continuous-flow anaerobic with an active volume of 20 dm3. The digestion process was run at 38 ± 1 °C. The experiment was divided into two stages. Raw (non-pretreated) MSS was used in stage 1, whereas the MSS used in stage 2 was pre-treated with SCO2. The SCO2/MSS ratio was 1:3. Each stage was sub-divided into four variants, with different levels of the OLR ranging from 2.0 to 5.0 gCOD/dm3·day. Pre-treatment with SCO2 was found to improve AD performance at an OLR of 3.0–4.0 gVS/dm3·day. The 3.0 gVS/dm3·day variant offered the best biogas production performance—both daily (29 ± 1.3 dm3/day) and per VS added (0.49 ± 0.02 dm3/gVS)—as well as the highest CH4 content in the biogas (70.1 ± 1.0%). In this variant, the highest energy output effect of 187.07 ± 1.5 Wh/day was obtained. The SCO2 pre-treatment was not found to change the pH, FOS/TAC, or the anaerobic bacterial community composition. Instead, these variables were mainly affected by the OLR. Our study shows that MSS pre-treatment with SCO2 at a SCO2/MSS ratio of 0.3 (by volume) significantly improves AD performance in terms of methane production and feedstock mineralization. The pre-treatment was found to have no negative effect on the long-term continuous operation of the reactor.