A Trombe wall with a phase change material (TW-PCM) is a practical and low-carbon passive solar heating method. However, the heat efficiency is not high due to the large amount of heat loss at night. Insulation on the outside of the cavity is a suitable solution, but the design method has not been obtained, which hinders the realization of zero energy buildings. In the present study, we analyzed the thermal performance of a TW-PCM with insulation on the outside of the cavity at nighttime to develop the design approach. A mathematical model was established and validated based on experiments. This model was used to analyze the heat efficiency in different outdoor climates for a TW-PCM with insulation on the outside of the cavity. As well, the solar heating fraction (SHF) was analyzed. The results indicated that insulation on the outside of the cavity could significantly improve the thermal performance due to the reduced heat loss during the nighttime. The recommended additional thermal resistance due to the insulation on the outside of the cavity was negatively correlated with the average outdoor air temperature in January based on the analysis of various climates in China. The thermal resistance of the closed air cavity, formed by the TW-PCM and the insulation component, at the same wall emissivity was similar under the recommended additional thermal resistance in different outdoor climates. The SHF was improved significantly for the TW-PCM buildings with insulation on the outside of the cavity and it had a linear relationship with the solar heating load ratio (SLR).