Although numerous studies have demonstrated the toxic effects of fine particulates less than 2.5 µm (PM2.5) on the health of humans, little information is available on the ecotoxicity of PM2.5. Water-soluble inorganic ions (WSII, including Na+, NH4+, K+, Mg2+, Ca2+, Cl−, NO3−, and SO42−) can compose more than 60% of PM2.5. To better understand the possible impacts of WSII-PM2.5 on leaf litter decomposition, we conducted an experiment in which two leaf litters from oak (Quercus variabilis) and pine (Pinus massoniana) dominant forests in subtropical China were incubated in microcosms containing their respective forest soils and treated with WSII-PM2.5. Our results showed that, after six-months of decomposition, the WSII-PM2.5 treatments inhibited leaf litter decomposition rates, carbon and nitrogen loss, microbial biomass, and enzyme activities in the two forests. In addition, higher WSII-PM2.5 concentration led to stronger negative effects. Comparative analysis showed that the negative effects of WSII-PM2.5 on oak forest were greater than on pine forest, relating to the higher susceptibility to changes of soil microenvironment in oak forests. WSII-PM2.5 may influence decomposition through soil acidification and salinization, which could also cause a sub-lethal depression in soil isopod activity. However, in the first month of decomposition, mass loss of the oak and pine leaf litters under the low concentration WSII-PM2.5 were 21.63% and 35.64% higher than that under the control, respectively. This suggests that transitory low concentrations of WSII-PM2.5 have a promoting effect on decomposition. Long-term PM2.5 exposure, therefore, may have profound ecosystem consequences by altering the balance of ecosystem carbon flux, nutrient cycling, and humus formation in the future.