With the significant growth in the number of PHEVs, conducting in-depth research on their CO₂ emission characteristics is essential. This study used the Horiba OBS-ONE Portable Emission Measurement System (PEMS) to measure the CO₂ emissions of three Plug-in Hybrid Electric Vehicle (PHEV) types: one Series Hybrid Electric Vehicle (S-HEV), one Parallel Hybrid Electric Vehicle (P-HEV), and one Series-Parallel Hybrid Electric Vehicle (SP-HEV), during real driving conditions. The findings show a correlation between acceleration and increased CO₂ emissions for P-HEV, while acceleration has a relatively minor impact on S-HEV and SP-HEV emissions. Under urban driving conditions, the SP-HEV displays the lowest average CO₂ emission rate. However, under suburban and highway conditions, the average CO₂ emission rates follow the order S-HEV > SP-HEV > P-HEV. An analysis of CO₂ emission factors across different road types and vehicle-specific power (VSP) ranges indicates that within low VSP intervals (VSP ≤ 0 for urban, VSP ≤ 5 for suburban, and VSP ≤ 15 for highway roads), the P-HEV exhibits the best CO₂ emission control. As VSP increases, the P-HEV’s emission factors rise under all three road conditions, with its emission control capability weakening when VSP exceeds 5 in urban, 15 in suburban, and 20 on highway roads. For the SP-HEV, CO₂ emission factors increase with VSP in urban and suburban areas but remain stable on highways. The S-HEV shows minimal changes in emission factors with varying VSP. This research provides valuable insights into the CO₂ emission patterns of PHEVs, aiding vehicle optimization and policy development.