This study was conducted from May 25 to June 6, 2009 at a downtown location (Centro) and an urban sector (Miravalle) site in the Metropolitan Zone of Guadalajara (MZG) in Mexico. The atmospheric concentrations of PM2.5 and its elemental and inorganic components were analyzed to identify their potential sources during the warm dry season. The daily measurements of PM2.5 (24 h) exceeded the WHO (World Health Organization) air quality guidelines (25 μg·m−3). The most abundant element was found to be Fe, accounting for 59.8% and 72.2% of total metals mass in Centro and Miravalle, respectively. The enrichment factor (EF) analysis showed a more significant contribution of non-crustal sources to the elements in ambient PM2.5 in Centro than in the Miravalle site. Particularly, the highest enrichment of Cu suggested motor vehicle-related emissions in Centro. The most abundant secondary ionic species (NO3−; SO42− and NH4+) and the ratio NO3−/SO42− corroborated the important impact of mobile sources to fine particles at the sampling sites. In addition, the ion balance indicated that particles collected in Miravalle experienced neutralization processes likely due to a higher contribution of geological material. Other important contributors to PM2.5 included biomass burning by emissions transported from the forest into the city.