The cardiothoracic ratio (CTR) and peripheral arterial occlusive disease (PAOD) are related to mortality in hemodialysis patients. However, data on the association between PAOD and CTR are limited. In this study, we aim to elucidate this relationship in patients on chronic hemodialysis. Using a retrospective cross-sectional study of 622 Taiwanese patients, we investigated the association of PAOD and CTR. PAOD was significantly associated with CTR in the crude analysis. The odds ratio (OR) for CTR >0.5 was 1.77 [95% confidence interval (CI), 1.32–2.37], and the odds ratio for CTR >0.6 was 2.18 [95% CI, 1.44–3.30]. After adjusting for confounding variables, this difference continued to exhibit significant predictive power for CTR >0.6 (OR, 1.88; 95% CI, 1.14–3.11), but the predictive power for CTR >0.5 was attenuated (OR, 1.41; 95% CI, 0.98–2.03). In the subgroup analysis, PAOD was an independent factor for CTR >0.6, particularly in elderly and female patients or patients with hemoglobin >10 mg/dl and with no history of cardiovascular disease. In this research, we showed that the detection of PAOD was independently associated with CTR >0.6 in patients on chronic hemodialysis.