The present study aims to assess arsenic accumulation and explore its association with renal function and bio-markers of CVD risk in chronic kidney disease patients receiving continuous ambulatory peritoneal dialysis (CAPD). The serum was collected from 87 CAPD patients and 26 healthy subjects between 2015 and 2016. The arsenic concentration was measured by inductively coupled plasma mass spectrometer. Clinical variables related to CVD risk were determined with automatic biochemical analyzer. Serum arsenic was higher in CAPD patients as compared to healthy volunteers. Moreover, significant differences of BMI, serum phosphorus, eGFR and Ccr were observed among groups. Positive correlation between serum arsenic and serum phosphorus was found (r = 0.453, p < 0.001). While serum arsenic was negatively associated with Ccr (r = -0.328, p = 0.002) and eGFR (r = -0.248, p = 0.020). The logistic regression models revealed that high serum arsenic was related to hyperphosphatemia (ORs, 1.827; 95%Cl, 1.145-2.913) after adjusted for the potential confounding factors. Overall, our findings inferred the accumulation of arsenic in CAPD patients. In addition, high serum arsenic was independently associated with the occurrence of hyperphosphatemia, which was a special and ubiquitous CVD risk factor in CAPD patients. This study provided a clue for the association between arsenic and CVD burden in CKD patients. At the same time, it suggested that prevention of arsenic accumulation should be taken into consideration clinically.