Between June 2018 and April 2019, a sampling campaign was carried out to collect PM2.5, monitoring meteorological parameters and anthropogenic events in the Sartenejas Valley, Venezuela. We develop a logistic model for PM2.5 exceedances (≥ 12.5 µg m−3). Source appointment was done using elemental composition and morphology of PM by scanning electron microscopy coupled with energy dispersive spectroscopy (SEM–EDS). A proposal of an early warning system (EWS) for PM pollution episodes is presented. The logistic model has a holistic success rate of 94%, with forest fires and motor vehicle flows as significant variables. Source appointment analysis by occurrence of events showed that samples with higher concentrations of PM had carbon-rich particles and traces of K associated with biomass burning, as well as aluminosilicates and metallic elements associated with resuspension of soil dust by motor-vehicles. Quantitative source appointment analysis showed that soil dust, garbage burning/marine aerosols and wildfires are three majority sources of PM. An EWS for PM pollution episodes around the Sartenejas Valley is proposed considering the variables and elements mentioned.