Expanded polystyrene concrete (EPSC) is increasingly utilized in buildings as a green building material. To investigate the effect of high-tenacity polypropylene (HTPP) fibers on the carbonation resistance (CR) of EPSC, five groups of EPSC specimens with HTPP fiber volume fractions of 0%, 0.6%, 0.9%, 1.2%, and 1.5% were prepared. Rapid carbonation tests were conducted to measure the carbonation depth (CD) and uniaxial compression strength (UCS) of the specimens at different carbonation ages (3, 7, 14, and 28 days). The CD and UCS of the specimens were calculated and analyzed. The results indicated that the HTPP fibers dramatically improved the CR of EPSC, with a decrease in the CD of up to 29.5% at 28 days. A model for predicting the CD of EPSC was developed. The model for the strength after carbonation also showed good agreement with the experimental results. Scanning electron microscopy (SEM) was used to examine the microstructure of the HTPP-reinforced EPSC, while the mechanism of HTPP fibers to enhance the CR of EPSC was elucidated. The findings of this study provide valuable insights for the application of EPSC as a structural material.