Sheet Molding Compound (SMC) materials are extensively utilized as high-voltage insulation materials in electrical equipment. SMC materials are prone to aging after long-term operation. Conducting non-destructive testing to assess their electrical and physicochemical properties is crucial for the safe operation of electrical equipment. This study identifies the optimal equipment parameters for testing SMC materials using Laser-Induced Breakdown Spectroscopy (LIBS) technology through experimental investigation and also explores the ablation characteristics of SMC under various laser parameters. The results indicate a significant positive correlation between the ablation depth and laser pulse number, while there is no correlation with single laser pulse energy. However, the ablation area demonstrates a strong positive correlation with both single laser pulse energy and laser pulse number. Additionally, LIBS spectral analysis provides elemental results comparable to Energy Dispersive Spectroscopy (EDS), facilitating the examination of variations in Na, Ti, Fe, Mg, Ca, and C elemental contents with depth. Moreover, an enhanced iterative Boltzmann plot method is suggested for calculating the plasma temperature using 21 Fe I spectral lines and the electron density using the Fe II 422.608 nm line. The variations of these plasma parameters with laser pulse number are documented, and the results show consistent trends, confirming that the laser-induced SMC plasma adheres to local thermodynamic equilibrium.