The deposition of ash on a diesel particulate lter (DPF) results in an increase in pressure drop across aftertreatment system, which leads to reduced capacity for soot and an increase in frequency of regeneration to eliminate the soot. To estimate the amount of ash and design a reduction method for the accumulated ash on the DPF, a deeper understanding of the ash generation mechanism is required.Previous studies have found that ash sampled at exhaust manifolds mainly comprises typical metal oxides, whereas ash accumulated on DPFs primarily comprises typical metal sulfates. However, the conversion mechanism from metal oxides to metal sulfates is not well understood. Herein, the formation mechanism of calcium sulfate (CaSO 4 ), which is the main component of ash on DPFs, was investigated using a ow reactor. Calcium oxide (CaO), which is the main component of ash sampled at exhaust manifolds, was made to react with SO 2 , SO 3 , O 2 , and H 2 O, when passed through a diesel oxidation catalyst. Quantitative analysis of the ash components in the products was performed using highperformance liquid chromatography. The concentrations of SO 2 , SO 3 , and H 2 O during the reaction were analyzed by Fourier-transform infrared spectroscopy. Based on the experimental results, it was found that CaSO 4 mainly formed from the reaction of CaO with SO 2 and SO 3 ; whereas, H 2 O inhibited CaSO 4 formation owing to the change in physicochemical properties of CaO.