The potential levels of exposure to indoor overheating in an urban environment are assessed for vulnerable social housing residents. Particular focus is given to the synergistic effects between summertime ventilation behaviour, indoor temperature and air pollutant concentration in relation to energy retrofit and climate change. Three different types of social housing are investigated (1900s’ low-rise, 1950s’ mid-rise and 1960s’ high-rise). The case study dwellings are located in Central London and occupied by vulnerable individuals (elderly and/or people suffering from ill-health or mobility impairment). Indoor temperature monitoring suggests that occupants are already exposed to some degree of overheating; the highest levels of overheating occur in 1960s’ high-rise tower blocks. The thermal and airflow performance simulation of a mid-floor flat in the 1960s’ block under the current and projected future climate indicates that improved natural ventilation strategies may reduce overheating risk to a certain extent, with night cooling and shading being slightly more effective than all-day rapid ventilation. However, their potential may be limited in future due to high external temperatures and the undesired ingress of outdoor pollutants. This highlights the need for the development of combined strategies aiming to achieve both indoor thermal comfort and air quality.