This study estimates the service life of concretes containing supplementary cementitious materials (SCM) subjected to carbonation from a probabilistic and reliability-based perspective. The aim is to enhance understanding of the risks associated with degradation and to propose an alternative approach for estimating the durability of reinforced concrete (RC) structures. The inclusion of supplementary cementitious materials (SCMs) is crucial for making concrete more sustainable, as these materials can reduce the carbon footprint of concrete production and improve its durability. Using available natural carbonation data from the literature on samples containing SCM, computational codes were developed for reliability analyses via the Monte Carlo Simulation method. The results indicated that all concrete samples exhibited a 100% probability of failure for coverages of 20 mm and 25 mm at an age of 100 years. For a coverage of 30 mm, all samples maintained a failure probability of over 98% within the same period. Notably, concretes incorporating metakaolin showed a substantial reduction in failure probability across all evaluated time periods, indicating superior durability compared to other samples. These findings significantly contribute to a deeper understanding of concrete degradation processes and provide valuable insights for the design and maintenance of RC structures, particularly in the context of using SCM. By adopting a probabilistic approach, the study underscores the importance of considering variability and uncertainties in predicting concrete durability, ultimately aiding in the development of more resilient and long-lasting infrastructure.