Trombe walls (TW) have been an effective passive solar technology for enhancing building energy efficiency. Considering the thermal storage and regulation capabilities of phase change materials (PCM) in solar energy utilization, TW with PCM (PCMTW) were designed and optimized to further improve building energy performance. This study investigated the combined effects of PCM phase change temperature, PCM location and ventilation strategies on a single-layer PCMTW. Moreover, a novel double-layer PCMTW was proposed and evaluated across various climate regions of China in consideration of the effect of PCM phase change temperature combinations. Results show that the single-layer PCMTW with PCM22 placed next to inner surface and ventilation achieved the lowest annual energy consumption. The selection of PCM phase change temperature was crucial for various climatic conditions. Compared to the traditional building, the highest heating energy-saving was 118.16 kWh/m2 achieved in Changchun with PCM22 + 28, and the highest cooling energy-saving was 45.71 kWh/m2 achieved in Haikou with PCM25 + 28. Additionally, the double-layer PCMTW was recommended for climate regions where the daily average temperature and the daily average solar emissivity were 20–25 °C and below 4 kWh/m2 in summer, and below 10 °C and 2–6 kWh/m2 in winter.