This paper reports the development of a practical exercise carried out with first-year students of the Master's Degree in Product Design (MDP) at the Lisbon School of Architecture (FAULisboa), in the Materials and Prototyping course unit, focused on acquiring skills in digital manufacturing technologies and search for more sustainable materials. Currently, the complexity of design activity has been supported by these technologies for the development of products, services and systems, applied in the different phases of the design process, considering the compatibility of materials and Industry 4.0 technologies. The aim of our research is to explore the creative potential of digital manufacturing in the design process, in particular in the development of customised and flexible modular system solutions and the selection of the most sustainable materials. As a method to support this research we carried out a case study, combining a systematic review of literature with empirical research, based on an exercise, which aims to answer the following questions: How to prototype? Why prototyping? Which materials to prototype? As a result of this exercise and after the phases of Theoretical knowledge, Applied knowledge and Reflection, carried out by the students, we concluded that digital manufacturing technologies make it possible to experience alternative and creative solutions, with diverse materials, considering customised solutions. That provided guidance on a pedagogical practice based on experimental and creative strategies applied to teaching digital manufacturing materials and processes for Product Design, highlighting the importance of these technologies in supporting innovation-oriented design activity.