Esotropia, which is the medial deviation of one or both eyes, is a rare withdrawal symptom that has been associated with opiate addiction. We report a case of a 36-year-old female patient who developed acute-onset esotropia and diplopia after self-admission to a psychiatric facility for fentanyl addiction treatment and a systematic review of this rare presentation. A search of four databases (PubMed, Scopus, Embase, and Google Scholar) was conducted as of January 2024. We found 15 documented cases of opiate withdrawal-associated esotropia, with an average age of 27.2 years and an average time between last use and symptom onset of 5.61 days. The most common symptom was diplopia, especially binocular diplopia, and the majority of cases resolved without pharmacologic intervention. Considering the current opioid crisis, our systematic review and case report add valuable insight into the less-explored neurological and ophthalmological consequences of opiate withdrawal, a condition that should always be considered in cases of acute or chronic onset esotropia.