The study followed 158 patients with chronic pelvic pain of venous origin (VO-CPP) who underwent ovarian vein embolization combined with polidocanol sclerotherapy. Technical success was achieved in 100% of cases, and most patients experienced significant pain relief within 3 months. Visual analogue scale (VAS) pain scores were significantly lower after the procedure than before (p < 0.001). Clinical efficacy was 83.5% at 6 months and 75.9% at final follow-up, with relapse occurring in 9.1% of patients (12/132) between 6 and 15 months. Independent risk factors for poor prognosis were parity ≥3 (OR 2.266; 95% CI: 1.034–4.969; p = 0.041) and estrogen-dependent diseases (OR 2.586; 95% CI: 1.177–5.680; p = 0.018). The complication rate was 7%, with pelvic vein thrombosis being the most common. The procedure is feasible and safe in the treatment of VO-CPP.