The new concept of virtual coupling (VC) envisages autonomous trains running in radio-connected platoons to significantly improve railway capacity and address the forecasted increase in railway demand. Such a concept will introduce radical changes to current train services, technologies, and procedures, which calls for a deeper understanding of the possible modes of operation and the impacts on the entire railway business. This paper investigates market potentials and operational scenarios of VC for different segments of the railway market: high-speed, main-line, regional, urban, and freight trains. The research builds on the Delphi method, with an extensive survey to collect expert opinions about benefits and challenges of VC as well as stated travel preferences in futuristic VC applications. Survey outcomes show that VC train operations can be very attractive to customers of the high-speed, main-line, and regional market segments, with benefits that are especially relevant for freight railways. In particular, customers of regional and freight railways are observed to be unsatisfied with current train services and willing to pay higher fares to avail of a more frequent and flexible service enabled by VC. Operational scenarios for VC are then defined by setting market-attractive service headways and by characteristics of the rolling stock, infrastructure, and traffic management. An analysis of strengths and weaknesses of such a concept together with business opportunities and threats is carried out. The defined VC future scenario is set to induce a sustainable shift of customers from other travel modes to the railways.