The Web of Data is an open environment consisting of a great number of large inter-linked RDF datasets from various domains. In this environment, organizations and companies adopt the Linked Data practices utilizing Semantic Web (SW) technologies, in order to publish their data and offer SPARQL endpoints (i.e., SPARQL-based search services). On the other hand, the dominant standard for information exchange in the Web today is XML. The SW and XML worlds and their developed infrastructures are based on different data models, semantics and query languages. Thus, it is crucial to develop interoperability mechanisms that allow the Web of Data users to access XML datasets, using SPARQL, from their own working environments. It is unrealistic to expect that all the existing legacy data (e.g., Relational, XML, etc.) will be transformed into SW data. Therefore, publishing legacy data as Linked Data and providing SPARQL endpoints over them has become a major research challenge. In this direction, we introduce the SPARQL2XQuery Framework which creates an interoperable environment, where SPARQL queries are automatically translated to XQuery queries, in order to access XML data across the Web. The SPARQL2XQuery Framework provides a mapping model for the expression of OWL-RDF/S to XML Schema mappings as well as a method for SPARQL to XQuery translation. To this end, our Framework supports both manual and automatic mapping specification between ontologies and XML Schemas. In the automatic mapping specification scenario, the SPARQL2XQuery exploits the XS2OWL component which transforms XML Schemas into OWL ontologies. Finally, extensive experiments have been conducted in order to evaluate the schema transformation, mapping generation, query translation and query evaluation efficiency, using both real and synthetic datasets.