CO2 enhanced oil recovery (CO2-EOR) project is of significance for CO2 sequestration and heavy oil recovery. Quantitative monitoring of CO2 saturation (SCO2) is essential to recognizing and understanding the migration and distribution of CO2 injected into the geological formations. In this paper, based on the difference in the neutron moderation ability of CO2, water and heavy oil, thermal neutron detection technique is applied in heavy oil reservoirs to monitor CO2 sequestration. By Monte Carlo simulation, the responses of thermal neutron count ratio versus different porosities and CO2 saturation were studied. Then, a mathematical model of CO2 saturation versus thermal neutron count ratio and formation porosity was established to quantitatively calculate CO2 saturation. Besides, the effects of formation pressure and temperature, heavy oil density, lithology, and other factors on the method were studied. Results show that variations of formation pressure, formation temperature, and density of heavy oil have little impact on the CO2 saturation measurement. However, the change of formation lithology results in larger CO2 saturation errors and needs corrections. In addition, the method has a low discrimination between CO2 and CH4 gas, and the results are easily affected by the CH4 content. Finally, a simulated case demonstrates the application of the method. For the heavy-oil sandstone with different porosities, the method shows a perfect performance: the SCO2 errors are less than 1% for the high and low gas saturated formation. This research provides an effective strategy to monitor CO2 storage and residual oil saturation in CO2-EOR reservoirs.