Rechargeable metal-ion batteries are considered promising electric storage systems to meet the emerging demand from electric vehicles, electronics, and electric grids. Thus far, secondary Li-ion batteries (LIBs) have seen great advances in terms of both their energy and their power density. However, safety issues remain a challenge. Therefore, rechargeable Al-ion batteries (AIBs) with a highly reliable safety advantage and active electrochemical performances have gathered intensive attention. However, the common issue for these two metal-ion batteries is the lack of cathode materials. Many advanced electrode materials reported provide greatly enhanced electrochemical properties. However, their inherent disadvantages—such as complicated fabrication procedures, restricted manufacturing parameters, and the requirement of expensive instruments—limits their potential for further applications. In this work, we demonstrate the high electrochemical activity of the lanthanide element, Sm, towards storing charges when used in both LIBs and AIBs. Lanthanide elements are often overlooked; however, they generally have attractive electrochemical properties owing to their unpaired electrons. We employed starch as both a low-cost carbon source and as a three-dimensional support for Sm metal nanoparticles. The composite product is fabricated using a one-pot wet-chemical method, followed by a simultaneous carbonization process. As a result, highly improved electrochemical properties are obtained when it is used as a cathode material for both LIBs and AIBs when compared to bare starch-derived C. Our results may introduce a new avenue toward the design of high-performance electrode materials for LIBs and AIBs.