One of the key objectives of knowledge management is to transfer knowledge quickly and efficiently from experts to novices, who are different in terms of the structural properties of domain knowledge or knowledge structure. This study applies experts’ semantic networks to hypertext navigation design and examines the potential of the resulting design, i.e., semantic hypertext, in facilitating knowledge structure acquisition and problem solving. Moreover, we argue that the level of sophistication of the knowledge structure acquired by learners is an important mediator influencing the learning outcomes (in this case, problem solving). The research model was empirically tested with a situated experiment involving 80 business professionals. The results of the empirical study provided strong support for the effectiveness of semantic hypertext in transferring knowledge structure and reported a significant full mediating effect of knowledge structure sophistication. Both theoretical and practical implications of this research are discussed.