Provided are hybrid active material structures for use in electrodes of electrochemical cells and methods of forming these structures. A hybrid active material structure comprises at least one first substructure and at least one second substructures, each comprising a different layered active material and interfacing each other. Combining multiple layered active materials into the same structure and arranging these materials in specific ways allow achieving synergetic effects of their desirable characteristics. For example, a layered active material, which forms a stable solid electrolyte interface (SEI) layer, may be form an outer shell of a hybrid active material structure and interface with electrolyte. This shell may surround another layered active material, which has a higher capacity but would otherwise forma a less stable SEI layer. Furthermore, multiple layered active materials may be arranged into a stack, in which one of these materials may operate as an ionic and/or electronic conductor.