Flue gas desulfurization (FGD) and selective catalytic reduction (SCR) technologies have been widely used to control the emissions of sulphur dioxide (SO2) and nitrogen oxides (NOX) from coal-fired power plants (CFPPs). Field measurements of emission characteristics of four conventional CFPPs indicated a significant increase in particulate ionic species, increasing PM2.5 emission with FGD and SCR installations. The mean concentrations of PM2.5 from all CFPPs tested were 3.79 ± 1.37 mg/m3 and 5.02 ± 1.73 mg/m3 at the FGD inlet and outlet, respectively, and the corresponding contributions of ionic species were 19.1 ± 7.7% and 38.2 ± 7.8%, respectively. The FGD was found to enhance the conversion of NH3 slip from the SCR to NH4+ in the PM2.5, together with the conversion of SO2 to SO42-, and increased the primary NH4+ and SO42- aerosol emissions by approximately 18.9 and 4.2 times, respectively. This adverse effect should be considered when updating the emission inventory of CFPPs and should draw the attention of policy-makers for future air pollution control.