Atmospheric aerosol particles (PM2.5) were collected from Taif city during 2011/2012. PM2.5 samples were collected on polycarbonate filters using a cyclonic collector. Energy Dispersive X-ray Fluorescence (EDXRF) was used for the elemental analysis of the PM2.5. The analysis resulted in detected concentrations for twenty five elements, namely; Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Se, Rb, Sr, Y, Ba, Ta, Pb and black carbon (BC). Fortunately, the measured concentrations of the potentially hazardous trace elements As, Cu, Cr, Mn, Ni and Pb were below the limits defined by international guidelines and national standards of ambient air quality. According to Electron Paramagnetic Resonance (EPR) measurements, three remarkable signals were detected and identified. Using Pearson’s correlation coefficients and Principal Component Analysis (PCA), it was possible to distinguish between natural and anthropogenic.