Product-Service (P-S) represents an innovative way to create highly sustainable solutions for both large and small enterprises. However, very few works propose structured approaches for P-S ideation and design in manufacturing industry. This paper presents a novel methodology to support ideation and preliminary design of sustainable P-S solutions within industrial chains involving Large Enterprises (LEs) as well as Small and Medium Enterprises (SMEs). It is based on a matrix-based approach and allows defining the P-S functional and ecosystem requirements according to the customer needs and sustainability principles. The research purpose is twofold: to effectively support industrial chains in P-S requirements elicitation, and to verify the benefits of P-S integration from the design stages in developing sustainable solutions. The research study involved an Italian company with its supply chains of SMEs, distributed in Europe, and aims at developing a new P-S idea in the white goods sector by exploiting Information and Communication Technologies (ICT).