Educational videos represent a valuable resource that can reduce teachers’ workload and allow students to have an alternative learning experience. However, for these videos to be educationally effective, they must follow established learning principles. Yet, for the structuring of educational videos it has not been sufficiently clarified empirically to what extent one structural sequence (example-rule, rule-example) is superior to the other in terms of learning success particularly in relation to learners’ prior knowledge. To investigate this connection and additional factors influencing the learning success, two identical educational videos on the law of interaction were developed, differing only in their structural sequence (example-rule, rule-example). These videos were embedded in a pre-post study with N = 258 students. Our findings indicate that the structural sequence has no influence on learning success in the context of the presented educational videos on the law of interaction. However, students’ prior knowledge along with other motivational factors play a significant role in students’ learning success.