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SIMS was used to distinguish the primary and secondary electrical short circuit (ESC) arc beads. A Cs⁺ primary ion was used to detect the ¹²C ⁻, ⁶³Cu ⁻, ¹⁸O ⁻ and ³⁷Cl ⁻ secondary ions formed during 0–3μm depth profiles. Thin surface layer enriched with C, Cl and O was observed in the primary arc beads, whereas a comparably thick layer of Cl was observed in the secondary arc beads at the 0–0.3μm depth profile. Comparative study of real case samples with those of simulated samples indicates that SIMS can be used as a complementary technique for identification of the cause of fire during fire investigation.