Reinforcement corrosion is a concern in the structural engineering domain, since it triggers several pathological manifestations, reducing the structural service life. Chloride diffusion has been considered one of main causes of reinforcements' corrosion in reinforced concrete. Corrosion starts when the chloride concentration at the reinforcements interface reaches the threshold content, leading to depassivation, whose assessment of its time of starts is a major challenge. This study applied the transient Boundary Element Method (BEM) approach for modelling chloride diffusion in concrete pores. The subregion BEM technique effectively represented the cracks inherent to the material domain, and environmental effects were also considered. Because of the inherent randomness of the problem, the service life was evaluated within the probabilistic context; therefore, Monte Carlo Simulation (MCS) assessed the probabilistic corrosion time initiation. Three applications demonstrated the accuracy and robustness of the model, in which the numerical results achieved by BEM were compared against numerical, analytical, and experimental responses from the literature. The probabilistic modelling substantially reduced the structural service life when the cracks length was longer than half of concrete cover thickness in highly aggressive environments.