We present an approach to enhancing information access through Web structure mining in contrast to traditional approaches involving usage mining. Specifically, we mine the hardwired hierarchical hyperlink structure of Web sites to identify patterns of term-term co-occurrences we call Web functional dependencies (FDs). Intuitively, a Web FD ‘x y’ declares that all paths through a site involving a hyperlink labeled x also contain a hyperlink labeled y. The complete set of FDs satisfied by a site help characterize (flexible and expressive) interaction paradigms supported by a site, where a paradigm is the set of explorable sequences therein. We describe algorithms for mining FDs and results from mining several hierarchical Web sites and present several interface designs that can exploit such FDs to provide compelling user experiences.