Samples of PM₁₀ and PM_2.5 were collected using High Vol and MiniVol devices on the platform of a subway station in Mexico City and in an outdoor location close to it, using such devices. Soluble extractable organic matter (SEOM) and water solubility of metals were determined. Elemental composition and solubility of trace metals were determined and individual aerosol particles were studied with scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDX). The concentration levels in both sizes were similar during all days with the exception of weekends, especially on Sunday when activity decreases due to lower trains’ frequency. The largest particles concentrations in the subway were found from 06:00 to 14:00 and the lowest concentrations were registered from 22:00 to 06:00. Concentrations of PM_2.5 ranging between 60 μg m⁻³ and 93 μg m⁻³ (10% and 90% percentile) in the subway were 6% larger than outside, whereas PM₁₀ were 20% larger than outside ranging from 88 μg m⁻³ to 145 μg m⁻³. Greater Fe, Cu, Ni, Cr and Mn concentrations were quantified in the subway samples as compared to the airborne particles by up to 2.5, 9, 1.8, 2.0 and 2.6 times, respectively. Even when the solubility percent of these metals in the subway PM was smaller than in the outdoor airborne particles, metals’ concentrations were greater. SEM and EDS exhibit the presence of many individual particles with a large metal content in the subway samples. Correlation analysis showed the influence of outdoor PM in the subway aerosols, but characterization revealed also important differences in the presence of metals and SEOM, due to underground sources such as friction, brake system, and metals from sparking. This means that a large number of commuters are exposed during labor days to large toxic metals concentrations as they transit.