XML documents are typically queried with a combination of value search and structure search. While querying by values can leverage traditional database technologies, evaluating structural relationship, specifically parent-child or ancestor-descendant relationship, between XML element sets has imposed a great challenge on efficient XML query processing.This paper proposes XR-tree, namely, XML Region Tree, which is a dynamic external memory index structure specially designed for strictly nested XML data. The unique feature of XR-tree is that, for a given element, all its ancestors (or descendants) in an element set indexed by an XR-tree can be identified with optimal worst case I/O cost. We then propose a new structural join algorithm that can evaluate the structural relationship between two XR-tree indexed element sets by effectively skipping ancestors and descendants that do not participate in the join. Our extensive performance study shows that the XR-tree based join algorithm significantly outperforms previous algorithms.