Several types of pollution episodes, including dust storm (DSs), haze dust (HDs), straw rice combustions (SRCs) are common phenomena and represent severe environmental hazard in Egypt. This study provides the first comprehensive analysis of the chemical characteristics of aerosol during air pollution episodes at an urban area in Giza, Egypt. PM2.5 samples during various PM episodes during 2013–2014 were collected and analyzed. Results indicate that the highest PM2.5 mass concentrations were found during DSs (250 μg/m3), followed by HDs (130 μg/m3) and SRCs (103 μg/m3). Average PM2.5 mass concentrations were 1.91, 3.68 and 1.68 times higher than on normal days (NDs) during HDs, DSs and SRCs, respectively. The highest total water-soluble ions concentration was 61.1 μg/m3 during HDs, followed by SRCs (41.9 μg/m3) and DSs (35.2 μg/m3). SO42- is the most abundant chemical components on the three PM episodes. Secondary inorganic ions (NO3−, SO42−, and NH4+) were enriched during HDs. The total secondary inorganic ions concentrations were 3.17, 1.39 and 1.75 times higher than NDs during HDs days, DSs days and SRCs days, respectively. PM from SRCs showed high K+ and Cl−. SO42-/K+, NO3−/SO42- and Cl−/K+ ratios proved effective as indicators for different pollution episodes. A Ca2+/Al ratio indicates that soil dust was dominant during DSs. Ion balance calculations indicated that PM2.5 from HDs was acidic, while the DSs and SRCs particles were alkaline and the NDs particle's was nearly neutral. The total crustal and anthropogenic metals concentrations were higher in DSs than other PM episodes and normal days. The enrichment factors values in PM episodes and normal days indicate that Fe and Mn in NDs, HDs, DSs and SRCs as well as Cr and Ni in DSs come mainly from crustal sources, whereas Cr, Ni, Co, Cu, Zn, Pb and Cd in PM episodes and NDs are anthropogenic.