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Primary hepatic squamous cell carcinoma (SCC) is extremely rare, and only a few dozen cases have been reported to date. It can barely be diagnosed before histopathological examination, which necessitates the exclusion of metastatic tumors. In this case, we present a 60-year-old female patient with no comorbidity. As laboratory tests and imaging examinations were not diagnostic, ultrasonography (US)-guided liver biopsy was performed and eventually revealed a definitive pathological diagnosis of hepatic SCC. After excluding metastasis, the diagnosis of primary hepatic SCC was established, and then chemotherapy and immunotherapy were performed. Additionally, a comprehensive literature search was conducted on primary hepatic SCC using PubMed, Google Scholar, and Web of Science, and a total of 53 articles were retrieved with a time range from 1972 to 2022. A critical analysis was then performed to evaluate previous literature focusing on the clinical characteristics, imaging features, treatments, and prognosis.