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In this study, the physicochemical and photocatalytic properties of two kinds of stannate perovskite oxides (MgSnO 3 and CaSnO 3) were investigated under simulated sunlight, where dimethyl phthalate (DMP) and diethyl phthalate (DEP) were selected as the probe pollutants. The results of photochemical characterization showed that MgSnO 3 perovskite exhibited better photocatalytic performance than CaSnO 3 perovskite. MgSnO 3 perovskite could effectively degrade 75% of DMP and 79% of DEP through pseudo-first-order reaction kinetics, which remained good in pH 3.0 to 9.0. Quenching experiments and electron paramagnetic resonance (EPR) characterization indicated that photogenerated holes (h +), superoxide (O 2 −), and hydroxyl radicals (OH) worked in the photo-degradation, while O 2 − played the most important role. Furthermore, intermediates identification and density functional theory (DFT) calculations were used to explore the degradation mechanism. For both DMP and DEP, the reactive oxygen species (ROS, including O 2 − and OH) were responsible for the hydroxylation of benzene ring and the breaking of the aliphatic chain, while h + was prone to break the aliphatic chain. This work is expected to provide new insights on the photocatalytic mechanism of stannate perovskites for environmental remediation. [Display omitted] • MgSnO 3 and CaSnO 3 perovskites were firstly used for photocatalytic degradation of PAEs. • MgSnO 3 perovskite exhibited better photocatalytic performance. • h + and O 2 − were the predominant radicals in photo-degradation. • Experiments and DFT calculations were combined to elucidate the degradation mechanism. [ABSTRACT FROM AUTHOR]