Air pollution is one of the most important problems in big cities, resulting in adverse health effects. The aim of the present study was to characterize the personal exposure to indoor and outdoor pollution in the Greater Athens Area in Greece by taking measurements during a journey from suburban to mixed industrial–urban areas, encompassing walking, waiting, bus travel, and metro travel at various depths. For this reason, low-cost (LC) sensors were used, and the inhaled dose of particulate matter with an aerodynamic diameter of less than or equal to 2.5 μm (PM2.5) in different age groups of passengers was calculated. Specific bus routes and the Athens metro network were monitored throughout different hours of the day. Then, the average particulate matter (PM2.5) exposure for a metro passenger was calculated and evaluated. By considering the ventilation rate of a passenger, an estimation of the total PM2.5 inhaled dose for males and females as well as for different age groups was made. The results showed that the highest PM2.5 concentrations were observed inside the wagons with significant increases during rush hours or after rush hours. Furthermore, there should be a concern regarding older individuals using the subway network in Athens during rush hours and in general for sensitive groups (people with asthma, respiratory and cardiovascular problems, etc.).