Plummer-Vinson syndrome (PVS), also called "Paterson-Brown-Kelly syndrome“, is a rare medical syndrome generally affecting middle-aged women. Iron deficiency anemia is the prime etiological factor and other probable factors include malnutrition, genetic predisposition, or autoimmune processes characterized by three distinctive features: iron deficiency anemia, dysphagia, and esophageal web. The dysphagia is generally painless and intermittent or progressive over years, restricted to solids, and associated with weight loss. The exact pathogenesis of PVS is still indistinguishable, but it is interconnected with iron deficiency anemia. Plummer-Vinson syndrome, if left untreated, carries an increased risk of developing squamous cell carcinoma of the upper alimentary tract.In this case report, a 40-year-old female patient presented long-standing dysphagia for months, which progressively developed to postcricoid squamous cell carcinoma by the time she approached to medical treatment. Diagnosis was confirmed through laboratory tests, showing iron deficiency anemia and whole-body positron emission tomography-computed tomography (PET-CT) presenting squamous cell carcinoma in postcricoid region (hypopharynx).