Over the last decade, we have witnessed an explosive growth in the information available on the Web. Today, Web browsers provide easy access to myriad sources of text and multimedia data. Search engines index more than a billion pages and finding the desired information is not an easy task. This profusion of resources has prompted the need for developing automatic mining techniques on Web, thereby giving rise to the term “Web mining” (Pal, Talwar, & Mitra, 2002). Web mining is the application of data mining techniques on the Web for discovering useful patterns and can be divided into three basic categories: Web content mining, Web structure mining, and Web usage mining. Web content mining includes techniques for assisting users in locating Web documents (i.e., pages) that meet certain criteria, while Web structure mining relates to discovering information based on the Web site structure data (the data depicting the Web site map). Web usage mining focuses on analyzing Web access logs and other sources of information regarding user interactions within the Web site in order to capture, understand and model their behavioral patterns and profiles and thereby improve their experience with the Web site. As citizens requirements and needs change continuously, traditional information searching, and fulfillment of various tasks result to the loss of valuable time spent in identifying the responsible actor (public authority) and waiting in queues. At the same time, the percentage of users who acquaint with the Internet has been remarkably increased (Internet World Stats, 2005). These two facts motivate many governmental organizations to proceed with the provision of e-services via their Web sites. The ease and speed with which business transactions can be carried out over the Web has been a key driving force in the rapid growth and popularity of e-government, e-commerce, and e-business applications. In this framework, the Web is emerging as the appropriate environment for business transactions and user-organization interactions. However, since it is a large collection of semi-structured and structured information sources, Web users often suffer from information overload. Personalization is considered as a popular solution in order to alleviate this problem and to customize the Web environment to users (Eirinaki & Vazirgiannis, 2003). Web personalization can be described, as any action that makes the Web experience of a user personalized to his or her needs and wishes. Principal elements of Web personalization include modeling of Web objects (pages) and subjects (users), categorization of objects and subjects, matching between and across objects and/or subjects, and determination of the set of actions to be recommended for personalization. In the remainder of this article, we present the way an e-government application can deploy Web mining techniques in order to support intelligent and personalized interactions with citizens. Specifically, we describe the tasks that typically comprise this process, illustrate the future trends, and discuss the open issues in the field.