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Emerging Web services technologies provide an open infrastructure for automated business interaction, thereby creating new opportunities for business actors to collaborate within a networked constellation of enterprises via the Internet. The basis for a viable network of Web services (the supporting information system of such a networked constellation of enterprises) is a value model that shows sound value propositions to all actors involved. Requirements engineering techniques can be developed to support: (1) exploring alternative business models, and (2) evaluating alternatives on their economic viability, leading into the design and implementation of technical systems. In this paper, we present a business-oriented approach supporting Web services idea exploration (BASSIE), which exploits the synergy between the agent- and goal-oriented i* framework and the value-based e3value framework. The approach iterates between exploration of structural alternatives and qualitative evaluation using i*, and quantitative modeling and evaluation of business value using e3value. The approach is illustrated with a real life case study in digital music distribution.