Squares in the urban historical built environment are public open spaces prone to the risk of terrorist acts, essentially because they are ideal soft targets and attract significant user densities. Risk assessment methods should consider how users behave in them, both before and during an accident (i.e., the evacuation process). In addition to squares’ morphology and layout, and considering that urban areas are more and more prone to the effects of increasing temperatures, outdoor climate conditions can alter the initial scenario. In fact, such conditions can lead users to gather in specific outdoor areas, where they can look for shadows and shelter. This work hence proposes a simulation-based approach to assess how differences in users’ behaviours in response to increasing temperatures and squares’ morphology can alter the risk of terrorist acts in an emergency evacuation. An agent-based model is developed to simulate the interactions between users, hazards and the historical built environment. The work considers four typological squares prone to terrorist acts since they host a special building attracting users in front of it. These squares are derived from the analysis of Italian historical contexts within the BE S2ECURe project. Users are generated in the public open space (thus, before the terrorist act) depending on the intended uses of the square and on the outdoor temperature, which is affected by the square’s morphology. Three different users’ behaviours are modelled to consider (or not) the effects of the outdoor temperature on users’ thermal acceptability levels in an increasing temperature situation. Then, two evacuation scenarios are simulated: (a) a general evacuation process, without attackers, as the baseline for the risk assessment; and (b) an armed assault with cold weapons, to define one of the most probable attack situations in open spaces. Evacuation performance indicators are developed to assess users’ risk. Preliminary verifications demonstrate the capabilities of the approach. The results show that higher differences in evacuation indicators are noticed in large and asymmetric squares, since their conditions highly affect the variability of users’ behaviours in response to increasing temperatures. At the same time, stronger safety behaviours in response to increasing temperatures could reduce emergency issues because they allow users to be more dispersed and initially placed farther from the attack area. Decision-makers could take advantage of the proposed approach and simulation tool, moving towards an effectiveness analysis of solutions to increase the thermal comfort of users in respect of the risk levels during an evacuation. Finally, applications to real-world scenarios are thus encouraged to compare such idealized results with effective conditions.