Primary hepatic squamous cell carcinoma (PHSCC), an exceptionally rare subtype of primary liver cancer, has been documented in fewer than 200 cases worldwide. Its diagnosis presents formidable challenges due to the absence of pathognomonic features, and it is frequently associated with an unfavorable prognosis. In this case, a 66-year-old female exhibited progressive dysphagia persisting for three months. A comprehensive diagnostic workup encompassing liver biopsy, contrast-enhanced abdominal CT, dual-phase gastrointestinal radiography, gastroduodenoscopy, and FDG-PET/CT confirmed PHSCC coexisting with secondary pseudoachalasia. To mitigate tumor burden and relieve extrinsic compression on the gastroesophageal junction, transarterial chemoembolization (TACE) targeting the left hepatic lesion was administered, utilizing a combination of chemotherapeutic agents (albumin-bound paclitaxel and cisplatin) and embolic microspheres. Given the lack of consensus guidelines for this orphan disease, advancing diagnostic precision and therapeutic innovations is imperative to optimize clinical outcomes.