Outpatient transesophageal echocardiography was performed in a 69‐year‐old man with a history of aortic valve repair. During the procedure the patient became markedly cyanotic and hypotensive. Oxygen saturation measured by pulse oximetry decreased from 97% to the mid‐80s. The man's condition continued to deteriorate. On transfer to a critical care unit, blood analysis by co‐oximetry showed methemoglobin saturation of 67.8%. The patient's condition improved significantly after intravenous administration of methylene blue 1 mg/kg. With increasing numbers of outpatient procedures performed under topical anesthesia, measures should be in place to deal with a potential life‐threatening adverse event such as methemoglobinemia.