Within the Green Analytical Chemistry paradigm, the best alternative for greening the methods of analysis comprises the direct determination of sample composition and/or sample properties without any chemical sample treatment, and, of course, it would be preferable not to have any physical treatment before acquisition of the information desired. In this review, we evaluate the state of the art in, and available alternatives for, analysis of solids without prior sample treatment, starting from the non-invasive quality control of products or processes through to the use of portable instruments for in situ determinations and the development of methods based on image analysis. We evaluate the advantages of such methodologies from the viewpoints of both environmental and operator risk.