Abstract: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a novel solid analysis technology, extensively utilized in geology, metallurgy, biology, and environmental studies among other fields. However, in LA-ICP-MS quantitative analysis of polymer samples, significant matrix effects exist, primarily attributed to differences in ablation behavior, resulting in sensitivity discrepancies and subsequently hindering accurate measurements. Currently, there is a paucity of research into the ablation behavior of such samples. This study selected four polymer samples with known concentrations of Pb, Cd, and Cr elements. The variances in ablation crater morphology under laser conditions of 193nm and 213nm wavelengths, and energy densities from 2.5 to 15 J·cm⁻² were studied using extended depth of field microscopy imaging technology. Also, their effects on signal stability and sensitivity were examined. The results demonstrate superior ablation behavior of the 193nm laser compared to the 213nm laser. At least three mechanisms causing matrix effect differences were identified in the laser ablation process of polymer samples, leading to element-related sensitivity variances. They are sputtering loss, ablation mechanism loss, and flocculation-sedimentation loss. Consequently, better analysis accuracy can be achieved by improving ablation behavior through energy density control and short-wavelength laser selection. Considerations such as thermal conductivity, which influences ablation behavior, should be factored in when selecting matrix-matched standards. The study of corresponding standard materials and ablation behavior should be prioritized in this field, to enhance the accuracy of measurements and foster the development of applications in this domain.