Wilkie's syndrome (superior mesenteric artery syndrome) is a rare cause of obstruction to the third part of duodenum due to compression between the superior mesenteric artery and the abdominal aorta. Pathologies like malignant growth in the mesenteric root, the presence of a lymph nodal mass compressing the terminal duodenum, dissecting aortic aneurysm, and intestinal malrotation may mimic the condition, but are not true etiologies of the syndrome. A duodenojejunal web causing narrowing of the duodenojejunal junction and mimicking Wilkie's syndrome has not been described before in the literature. We herein report a case of gastroduodenal obstruction due to a web in the duodenojejunal junction in a young female patient, which closely mimicked Wilkie's syndrome but was finally diagnosed postoperatively. We highlight the first case of its kind in an adult and discuss the challenges in both the diagnosis and management.