Volcanic exposure implies multiple hazards for human settlements. The identification of the potential hazards that volcanic activity can entail is a challenge requiring assessing the specific situations that a determined place would face. Popocatépetl, a volcano in the centre of México, represents a significant hazard source, and it is located within a densely populated region with more than 20 million people. Despite the existence of a colour-based volcano alert level system for the current activity of the volcano, it is relevant to assess which local scenarios are more likely depending on numerous variables, namely, related to the distance from the volcano. A semi-quantitative analysis was carried out based on existing hazard maps and considering the probability of occurrence of volcanic explosivity, taking the settlement of San Pedro Tlalmimilulpan as a case study. This analysis led to a hierarchised rank of hazards, providing a basis for analysing multiple scenarios through failure mode and event analysis, failure tree analysis and event tree analysis. This process facilitates the contextualisation of the multiple challenges and potential chains of events that emergency actions, namely, emergency evacuations, would face. The analysis of the critical paths can help to identify critical aspects that could hinder the post-event response.