The fast detection of classical contaminants and their distribution on high-voltage transmission line insulators is essential for ensuring the safe operation of the power grid. The analysis of existing insulator contamination has traditionally relied on taking samples during a power cut, taking the samples back to the lab and then testing them with elemental analysis equipment, especially for sugars, bird droppings, and heavy metal particulates, which cannot be analysed by the equivalent salt deposit density (ESDD) or non-soluble deposit density (NSDD) methods. In this study, a novel method called laser-induced breakdown spectroscopy (LIBS) offering the advantages of no sample preparation, being nearly nondestructive and having a fast speed was applied for the analysis of metal contamination. Several LIBS parameters (laser energy and delay time) were optimized to obtain better resolution of the spectral data. The limit of detection (LOD) of the observed elements was obtained using a calibration curve. Compared to calibration curves, multivariate analysis methods including principal component analysis (PCA), k-means and partial least squares regression (PLSR) showed their superiority in analyzing metal contamination in insulators. Then, the elemental distribution of natural pollution was predicted using LIBS to fully capture information about the bulk elements (Na, Ni, Cu, Mn, Ca, etc.) of entire areas with PLSR. The results showed that LIBS could be a promising method for accurate direct online quantification of metal contamination in insulators.