To understand the influence of P-containing compounds on particulate matter (PM) emissions from the combustion of agricultural residues, the combustion of cornstalk was performed with the addition of a phosphorus-based additive, namely, ammonium dihydrogen phosphate (NH4H2PO4), in a fixed-bed combustion system. Simultaneously the ash samples, including PM collected by a Dekati low-pressure impactor (DLPI) and residual ash, were analyzed with variant analytical techniques. It was found that NH4H2PO4 addition significantly reduced PM0.1 and PM0.1-1 yields but increased PM1-10 yields. The maximum PM, and PM1 reduction efficiency can reach up to 50% at an optimal P/K molar ratio equal to 1. Meanwhile, the addition of NH4H2PO4 to cornstalk changed the chemical composition of PM1 from being dominated by KCl and KOH/K2CO3 with a small amount of K2SO4 to a system dominated by KPO3 and KCl with a small amount of K2SO4. Simultaneously, the possible PM1 reduction mechanism was proposed. In addition, the residual ash after combustion was rich in K- and P-containing species, indicating a potential utilization as a fertilizer. It showed that the addition of NH4H2PO4 is a promising approach to reduce PM1 emissions during the combustion of agricultural biomass.