Analyses of the relationships between climate, air substances and health usually concentrate on urban environments because of increased urban temperatures, high levels of air pollution and the exposure of a large number of people compared to rural environments. Ongoing urbanization, demographic ageing and climate change lead to an increased vulnerability with respect to climate-related extremes and air pollution. However, systematic analyses of the specific local-scale characteristics of health-relevant atmospheric conditions and compositions in urban environments are still scarce because of the lack of high-resolution monitoring networks. In recent years, low-cost sensors (LCS) became available, which potentially provide the opportunity to monitor atmospheric conditions with a high spatial resolution and which allow monitoring directly at vulnerable people. In this study, we present the atmospheric exposure low-cost monitoring (AELCM) system for several air substances like ozone, nitrogen dioxide, carbon monoxide and particulate matter, as well as meteorological variables developed by our research group. The measurement equipment is calibrated using multiple linear regression and extensively tested based on a field evaluation approach at an urban background site using the high-quality measurement unit, the atmospheric exposure monitoring station (AEMS) for meteorology and air substances, of our research group. The field evaluation took place over a time span of 4 to 8 months. The electrochemical ozone sensors (SPEC DGS-O3: R2: 0.71–0.95, RMSE: 3.31–7.79 ppb) and particulate matter sensors (SPS30 PM1/PM2.5: R2: 0.96–0.97/0.90–0.94, RMSE: 0.77–1.07 µg/m3/1.27–1.96 µg/m3) showed the best performances at the urban background site, while the other sensors underperformed tremendously (SPEC DGS-NO2, SPEC DGS-CO, MQ131, MiCS-2714 and MiCS-4514). The results of our study show that meaningful local-scale measurements are possible with the former sensors deployed in an AELCM unit.