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Abstract Electrical machines are composed of FeSi3 laminated sheets that are stacked and insulated in order to reduce eddy current losses. The FeSi6.5 alloy exhibits lower magnetic losses than FeSi3, but its brittleness makes it difficult to process by conventional rolling; additive manufacturing may therefore represent a promising alternative. However, reproducing the laminated architecture by additive manufacturing requires a multimaterial approach, whereas current processes are still predominantly limited to single-material builds and multimaterial additive manufacturing remains an emerging field of development. This work investigates the interface and compatibility between a ceramic and the ferromagnetic FeSi6.5 alloy with the aim of fabricating laminated structures for electrical machines by laser powder bed fusion. An innovative system is presented that converts a single-material laser powder bed fusion machine into a multimaterial platform. The ZrO 2 –Y 2 O 3 ceramic was selected for its chemical and mechanical properties. A deposition strategy for ZrO 2 –Y 2 O 3 on FeSi6.5 without preheating was established using an energy density of 509 J/mm 3 . Results show that the interface consists of a 50 µm-thick zone formed by mixing of the two materials, exhibiting a hardness of about 520 HV, higher than that of FeSi6.5 and lower than that of ZrO 2 –Y 2 O 3 . It is further demonstrated that remelting cycles modify the grain size, hardness, and composition of this interfacial region. This diffusion zone is of particular interest for the production of FeSi6.5/interfacial-zone laminates allowing magnetic flux and magnetic losses reduction. Processing parameters for each material and the deposition strategy are detailed in this article.