This study developed a video playing system that incorporated two signaling devices, headings and table of contents, for supporting video learning and navigation. An experiment was conducted for understanding the effects of the system on learning and navigation performance of the immediate and delayed tests. Thirty participants were randomly assigned to three conditions: the structure heading group with the two signaling devices, the heading group with the heading device, and the control group without any signaling device. The results revealed several significant findings. First, the two signaling devices can effectively help learners remember the structural information, but not detailed video content. Second, the table of contents may be detrimental for learning and navigation when learners have enough time to view the whole video. Third, the table of contents is helpful for learners to quickly grasp the structural knowledge when they just have a little time to view the video. These findings are discussed and a new video playing system prototype is proposed.