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Introduction: The therapeutic effect of chemical lumbar sympathectomy (CLS) on ischemic diseases of the lower limbs varies greatly among individuals. The time to peak (TTP) response in contrast-enhanced ultrasound (CEUS) can reflect the perfusion disorder of the calf skeletal muscle and the collateral circulation. In this study we evaluated the predictive value of CEUS in patients treated with CLS for end-stage atherosclerotic occlusive disease of the lower extremity (ASO-LE). Methods: This was a prospective study that included patients with end-stage ASO-LE and moderate to severe pain who had undergone a CEUS examination and CLS procedure and who were observed for 12 months after surgery. The patients' characteristics and prognostic factors, including lower limb pain score, skin temperature, walking distance, and ulcer and gangrene healing, were recorded. Results: Fifty-eight patients with a mean age of 66.24 (range 58–78) years were included in the study, of whom 42 (71.41%) were men. Following the CLS procedure, the numerical rating scale (NRS)-measured pain decreased significantly, and the skin temperature of the affected limb increased significantly (P < 0.05). The satisfaction rate of lower limb pain relief 1 year after operation was 53.45%. Correlation analysis showed that preoperative TTP response was correlated with the NRS score and skin temperature of the affected limb at 6 months and 12 months post surgery (P < 0.05). The binary logistic regression analysis indicated that a longer preoperative TTP response was associated with a higher risk of poor pain relief after CLS (odds ratio 1.126, 95% confidence interval 1.058–1.205). The receiver operating characteristic curve showed that preoperative TTP response had a certain predictive value on CLS treatment effect, with a sensitivity and specificity of 81.5% and 83.9%, respectively. When the preoperative TTP response was > 77.5, the risk of poor response after CLS increased. Conclusions: Preoperative TTP response was able to predict the therapeutic effect of CLS to a certain extent, and thus may aid physicians in determining the choice of CLS treatment for patients with ASO-LE. Trial Registration: Chinese Clinical Trial Registry: ChicTR1900028424 (principal investigator: Yue Wu; date of registration: 21 December 2019). [ABSTRACT FROM AUTHOR]