Over the last years, e-Government applications have become indispensable in every country as they help stakeholders carry out tasks with the administration. However, and despite their growing usage, most of these applications are created through a developercentered approach instead of a user-centered one, using traditional development processes that do not fit well with the diversity of stakeholders and existing legislation that involve e-Government applications today. Besides, usability is an important clue in the development of such solutions, so a user-centered approach, combined with a successful stakeholder and legislation analysis, should be considered overall. This paper is focused on addressing these concerns, and it provides a set of prescribed activities, tasks and products to be carried through a user-centered process in order to design usable web-based e-Government solutions. Specifically, our approach considers requirements engineering activities enhancing usability by analyzing the diversity and interests of the stakeholders involved, as well as the specific legislation as a source of organizational requirements. In addition, a validation is provided through a case study, showing the feasibility of the approach presented.