Atmospheric PM2.5 samples from Wuhan, China were collected during a winter period of February and a summer period of August in 2018. The average PM2.5 mass concentration in winter reached 112 μg/m3—about two-fold higher than that found in summer. Eight ionic species constituted 1/3 of PM2.5, whereas more than 85% represented secondary ionic aerosols (NO3−, SO42− and NH4+). Higher ratios of NO3−/SO42− (0.95–2.62) occurred in winter and lower ratios (0.11–0.42) occurred in summer showing the different contribution for mobile and stationary sources. Seventeen elemental species constituted about 10% of PM2.5, with over 95% Na, Mg, Al, Ca, Fe, K and Zn. Higher K-concentration occurred in winter indicating greater contribution from biomass and firework-burning. Carcinogenic risks by Cr, As, Cd, Ni and Pb in PM2.5 indicated that about 6.94 children and 46.5 adults among per million may risk getting cancer via inhalation during surrounding winter atmospheric sampling, while about 5.41 children and 36.6 adults have the same risk during summer. Enrichment factors (EFs) and elemental ratios showed that these hazardous elements were mainly from anthropogenic sources like coal and oil combustion, gasoline and diesel vehicles.