China’s LNG import volume in 2021 reached 121.356 million tons, which makes China the largest importer in the world. The ambient air vaporizer (AAV) for LNG vaporization is an ideal selection for minimizing the average monetary value of terminals and maximizing operating efficiency. However, the heat and mass transfer performance of real multi-component LNG is not the same as that of the pure component in AAV; what is more, deep cryogenic and multi-component characteristics of LNG could lead to the deterioration of heat-transfer performance, which may cause catastrophic consequences. Thus, this difficulty should be concerning and solved in its operation. Based on the law of conservation of energy and mass, a heat and mass transfer model was established that can calculate the coupled heat transfer from the LNG to the air-side of the AAV along its own length. Empirical correlations are proposed to predict some basic properties of the frost layer at the outside of the tube, where the internal fluid is seen as a pure component and a multi-component. The numerical results show that the root−mean−square error (RMS) of the frost thickness is 0.749 mm, and the RMS of the outlet fluid temperature is 2.06 K and 2.21 K in summer and winter, respectively. That is in good agreement with the experimental data in the previous literature. The results show that the length of the finned tube in the AAV affected by pure CH4 was increased by 42.5%; therefore, we recommend shortening the finned tube on the basis of safety to save costs. Compared to the pure components reference experiments, when the CH4 content of multi-component in five regions was 78.48−96.91%, it is found that the different varieties of thermodynamic dryness degree x within the two types of components is the key point for the distinct mechanisms of the heat transfer characteristics of the AAV. Additionally, compared to changing the design pressure and flow rate, it is found that varying the flow rate has a much greater impact on the heat and mass transfer performance of the AAV than changing its pressure. The calculation of the coupled heat and mass transfer of the AAV can provide a theoretical basis for subsequent engineering designs.