Growing concern about photothermal tumor therapy (PTT) as a promising alternative to conventional liver cancer treatment, which is a treatment strategy that utilizes near‐infrared (NIR) light‐induced photothermal agents (PTAs) to yield photothermal effects to localize thermal damage for tumors. Herein, given the gap between experimental research and clinical application, this review seeks to timely summarize and highlight the recent progress of PTAs used for photothermal treatment of liver cancer in vivo and in vitro in the last five‐year. The implications of various PTAs on the multifunctional photothermal conversion capability, the structure‐performance correlations of PTT, together with the evaluation of their potential in application are systematically dissected to further dig out what the buried mechanism is. Besides, higher requirements are put forward for the discrepancies and crucial issues faced by different PTAs in PTT with related medical technical obstacles being conquered, which lays a solid theoretical foundation for the medical field of oncology treatment as a whole, especially liver cancer. Finally, it is expected that this review can present valuable guidance for the design of efficient, photostability, and biosafety‐aware PTAs for anticancer therapy while stepping into the fast traffic lane for the conversion from bench to bedside in the foreseeable future. This review systematically summarizes the research progress of PTAs in the photothermal treatment of liver cancer in the past five years. The implications of various PTAs on the multifunctional photothermal conversion capability, the structure‐performance correlations of PTT, and the evaluation of their potential application are dissected. Moreover, the prospect and challenges of high‐efficiency combined photothermal therapy are also proposed.