Particulate organic matter (POM) has a significant enrichment effect on cadmium (Cd) of polluted soil, but it is unclear whether the Cd enrichment and availability of POM are influenced by soil physicochemical properties. In the present study, a total of 9 long-term Cd polluted agricultural soils were sampled from different provinces in China. The POM fractions with different particle sizes were physically separated from soils, and the multiple linear stepwise regression models were used to study the relationship between POM-Cd and EDTA-Cd with soil physicochemical properties. The results show that the contents of 2000–250 μm and 250–53 POM fractions were 2.21–21.1 g/kg and 8.85–36.1 g/kg, respectively. The contents of 2000–250 μm POM fractions were negatively correlated with soil total iron content, while the contents of 250–53 μm POM fractions were positively corelated with soil organic matter content. The POM-Cd concentrations were 2.06–5.33 times higher than the total Cd concentrations of soils, indicating the significant Cd enrichment of POM. After 24 hours extraction, 54.0–87.8% of POM-Cd could be extracted by EDTA. Soil pH was significantly positively correlated with the 2000–53 μm POM-Cd concentration and EDTA-Cd concentration, and the 250–53 μm POM-Cd concentration and EDTA-Cd concentration were also significantly positively correlated with soil total Cd concentrations. The increase in soil silt content would decrease the content of 2000–250 μm POM-Cd, and the increase in soil clay content would decrease the extraction rate of POM-Cd by EDTA extractant. Overall, the Cd enrichment and availability of POM are significantly affected by soil physicochemical properties, which is of great significance for understanding the mechanism of Cd migration and transformation in polluted soil and the application of subsequent remediation technologies.