Mobile devices are becoming an indispensable part of the daily lives and learning habits of older adults with the easy access of the Internet. It enhances the connection between old users and online education, which supplies an approach to cultivate them with innovative concepts and entrepreneurship of education. However, the complicated navigation of information systems (IS) confuses older adults, and gets them disoriented in searches of information, in addition, to influencing online activities for older adults. This study aims to investigate what kind of navigation of IS is suitable for older adults. A 2 × 2 (2 factors, 2 levels) mixed experimental design was employed. The two factors were, respectively, cognitive load (CL) and navigation structure (NS). A sample of 40 older participants (mean age = 64.37, SD = 4.03) performed online learning tasks in terms of innovative concept using linear hierarchical or mixed NSs under different time pressures. The results showed that linear hierarchical navigation is more appropriate for the elderly when learning and generating innovative concepts on smartphones, as the interaction between CL and NS exists. Overall, the findings combined suggest that the linear hierarchical NS, compared to mixed hierarchical navigation, obtained better usability in terms of task efficiency, CL, and subjective ratings. The findings can provide theoretical support for designers to design and develop mobile websites for older adults.