Vision-Language Navigation (VLN) is a challenging task which requires an agent to align complex visual observations to language instructions to reach the goal position. Most existing VLN agents directly learn to align the raw directional features and visual features trained using one-hot labels to linguistic instruction features. However, the big semantic gap among these multi-modal inputs makes the alignment difficult and therefore limits the navigation performance. In this paper, we propose Actional Atomic-Concept Learning (AACL), which maps visual observations to actional atomic concepts for facilitating the alignment. Specifically, an actional atomic concept is a natural language phrase containing an atomic action and an object, e.g., ``go up stairs''. These actional atomic concepts, which serve as the bridge between observations and instructions, can effectively mitigate the semantic gap and simplify the alignment. AACL contains three core components: 1) a concept mapping module to map the observations to the actional atomic concept representations through the VLN environment and the recently proposed Contrastive Language-Image Pretraining (CLIP) model, 2) a concept refining adapter to encourage more instruction-oriented object concept extraction by re-ranking the predicted object concepts by CLIP, and 3) an observation co-embedding module which utilizes concept representations to regularize the observation representations. Our AACL establishes new state-of-the-art results on both fine-grained (R2R) and high-level (REVERIE and R2R-Last) VLN benchmarks. Moreover, the visualization shows that AACL significantly improves the interpretability in action decision.