During the last decade, smart materials have increasingly impacted on several niches, among which that of one-off/limited edition experimental fashion. Thanks to their performativity, due to the implementation of Smart Materials Systems, they have reached indeed catwalks as well as museums and galleries. As boundaries between what-is-art and what traditionally was not supposed to be art are now turning into osmotic membranes, zooming on how smart materials are highly contributing to outline the new creative landscape can provide with interesting and compelling issues. Introducing three different areas of experimental fashion, named Multi-sensory dresses, Empathic dresses, and Bio-smart dresses and accessories, respectively covering the world of in-Lab experiments and design collaborations in relation to the application of advanced smart materials systems, the article discuss some of the implications in term of Design Thinking and Design Aesthetics.