Sustainability assessments can play an important role in decision making. This role starts with selecting appropriate methods for a given situation. We observed that scientists, consultants, and decision-makers often do not systematically perform a problem analyses that guides the choice of the method, partly related to a lack of systematic, though sufficiently versatile approaches to do so. Therefore, we developed and propose a new step towards method selection on the basis of question articulation: the Sustainability Assessment Identification Key. The identification key was designed to lead its user through all important choices needed for comprehensive question articulation. Subsequently, methods that fit the resulting specific questions are suggested by the key. The key consists of five domains, of which three determine method selection and two the design or use of the method. Each domain consists of four or more criteria that need specification. For example in the domain “system boundaries”, amongst others, the spatial and temporal scales are specified. The key was tested (retrospectively) on a set of thirty case studies. Using the key appeared to contribute to improved: (i) transparency in the link between the question and method selection; (ii) consistency between questions asked and answers provided; and (iii) internal consistency in methodological design. There is latitude to develop the current initial key further, not only for selecting methods pertinent to a problem definition, but also as a principle for associated opportunities such as stakeholder identification.