The efficacy and safety of gonadal vein embolization (GVE) with coils in the treatment of pelvic venous disease (PeVD) has not been fully investigated, and the outcomes after GVE do not always meet expectations of both doctors and patients. The study was aimed at assessing the incidence and causes of the complications after GVE with coils in patients with PeVD. This retrospective cohort study included 150 female patients with PeVD who underwent GVE with coils in 2000-2020. A total of 4975 patients with chronic pelvic pain (CPP) were examined, of which 1107 patients had the PeVD-related CPP and 305 underwent surgical or endovascular interventions on the gonadal veins. Complication rates were evaluated 30 days after GVE and classified according to the Society for Interventional Radiology (SIR) adverse event classification system. The pain severity before and after GVE was assessed using a visual analogue scale (VAS). All patients underwent duplex ultrasound after GVE, while patients with persisting pain syndrome and suspected perforation of the gonadal vein were also evaluated using computed tomographic venography. At 30 days after GVE, the CPP was decreased in 109 (72.6%) patients (from 8.2 ± 1.5 at baseline to 1.7 ± 0.8 scores, = 0.0001) and persisted in 41 (27.4%) patients (mean change from 8.1 ± 0.7 at baseline to 7.8 ± 0.4 scores; = 0.71). Post-embolic syndrome (PES) occurred in 22% of patients and was completely resolved in 1 month after GVE. The efficacy of GVE in the CPP relief after resolving PES was 94.6%. The GVE complications were identified in 52 (34.6%) patients. Minor complications included access-site hematoma (4%) and allergic reactions (1.3%), and major complications included protrusion of coils (5.3%), thrombosis of the parametrial/uterine veins (21.3%) and deep veins of the calf (2.7%). Gonadal vein embolization with coils in the treatment of PeVD is associated with the development of specific complications and adverse events. The most common complication was pelvic vein thrombosis. Post-embolization syndrome should be considered as an adverse event of this procedure.