Abstract Safety issues remain a major obstacle toward large‐scale applications of high‐energy lithium‐ion batteries. Embedding thermo‐responsive polymer switching materials (TRPS) into batteries is a potential strategy to prevent thermal runaway, which is a major cause of battery failures. Here, thin, flexible, highly responsive polymer nanocomposites enabled by bio‐inspired nanospiky metal (Ni) particles are reported. These unique Ni particles are synthesized by a simple aqueous reaction at gram‐scale with controlled surface morphology and composition to optimize electrical properties of the nanocomposites. The Ni particles provide TRPS films with a high room‐temperature conductivity of up to 300 S cm −1 . Such TRPS composite films also have a high rate (<1 s) of resistance switching within a narrow temperature range, good reversibility upon on/off switching, and a tunable switching temperature ( T s ; 75 to 170 °C) that can be achieved by tailing their compositions. The small size (≈500 nm) of Ni particles enables ready fabrication of thin and flexible TPRS films with thickness approaching 5 µm or less. These features suggest the great potential of using this new type of responsive polymer composite for more effective battery thermal regulation without sacrificing cell performance.