Perceiving multi-modal information and fulfilling dialogues with humans is a long-term goal of artificial intelligence. Pre-training is commonly regarded as an effective approach for multi-modal dialogue. However, due to the limited availability of multi-modal dialogue data, there is still scarce research on multi-modal dialogue pre-training. Yet another intriguing challenge emerges from the encompassing nature of multi-modal dialogue, which involves various modalities and tasks. Moreover, new forms of tasks may arise at unpredictable points in the future. Hence, it is essential for designed multi-modal dialogue models to possess sufficient flexibility to adapt to such scenarios. This paper proposes PaCE, a unified, structured, compositional multi-modal dialogue pre-training framework. It utilizes a combination of several fundamental experts to accommodate multiple dialogue-related tasks and can be pre-trained using limited dialogue and extensive non-dialogue multi-modal data. Furthermore, we propose a progressive training method where old experts from the past can assist new experts, facilitating the expansion of their capabilities. Experimental results demonstrate that PaCE achieves state-of-the-art results on eight multi-modal dialog benchmarks.