The gasification of liquefied natural gas (LNG) is characterized by a substantial release of cold energy, which can be utilized for power generation via thermoelectric generator (TEG). Employing a gasifier integrated with a thermoelectric generator for LNG gasification allows for the recovery of cold energy and its conversion to useful power, a process that holds significant potential for widespread application. In the study, a thermoelectric model has been developed for an annular thermoelectric module, which formed a new category of gasifier tube. The influence of the module’s structure as well as the heat transfer parameters on the thermoelectric performance was examined. The results revealed that an optimum height of the thermoelectric leg, specifically 2 mm, maximized the output power while allowing the thermoelectric conversion efficiency to reach a peak of 3.25%. Another noteworthy finding is that an increase in the central angle of the thermoelectric leg leads to a concomitant rise in output power but a decrease in conversion efficiency. Furthermore, when the heat transfer coefficients at the hot and cold ends of the module achieved 4000 W/(m2·K) and 10,000 W/(m2·K), respectively, the conversion efficiency can be elevated to 6.98%. However, any additional enhancement in power generation performance derived from further augmenting the heat transfer is marginal. These findings can serve as a valuable reference in the design and optimization of TEG intended for the recovery of cold energy from LNG.