To assess environmental exposures at the individual level, new assessment methods and tools are required. We developed an exposure assessment system (ExpoApp) for smartphones. ExpoApp integrates: (i) geo-location and accelerometry measurements from a waist attached smartphone, (ii) data from portable monitors, (iii) geographic information systems, and (iv) individual's information. ExpoApp calculates time spent in microenvironments, physical activity level, inhalation rate, and environmental exposures and doses (e.g., green spaces, inhaled ultrafine particles- UFP). We deployed ExpoApp in a panel study of 158 adults from five cities (Amsterdam and Utrecht- the Netherlands, Basel- Switzerland, Norwich- UK, and Torino- Italy) with an UFP monitor. To evaluate ExpoApp, participants also carried a reference accelerometer (ActiGraph) and completed a travel-activity diary (TAD). System reliability and validity of measurements were evaluated by comparing the monitoring failure rate and the agreement on time spent in microenvironments and physical activity with the reference tools. There were only significant failure rate differences between ExpoApp and ActiGraph in Norwich. Agreement on time in microenvironments and physical activity level between ExpoApp and reference tools was 86.6% (86.5–86.7) and 75.7% (71.5–79.4), respectively. ExpoApp estimated that participants inhaled 16.5 × 1010 particles/day of UFP and had almost no contact with green spaces (24% of participants spent ≥30 min/day in green spaces). Participants with more contact with green spaces had higher inhaled dose of UFP, except for the Netherlands, where the relationship was the inverse. ExpoApp is a reliable system and provides accurate individual's measurements, which may help to understand the role of environmental exposures on the origin and course of diseases.