Laser-induced breakdown spectroscopy was applied for real-time identification of different types of plastics. The plasma emission spectra of polypropylene, acrylonitrile–butadiene–styrene, polystyrene, and polyethylene terephthalate, the most commonly used plastics in black household appliances, were studied. It was confirmed that the C/H spectral line intensity ratio varies depending on the type of plastics. Aliphatic and aromatic polymers were discriminated owing to the presence of delocalized C–C bonds in the aromatic fragments, revealing a correlation between the chemical structure and emission of the C2 Swan bands. Plastics containing a heteroatom could be selectively detected by monitoring the emission line characteristics of the heteroatom. Four types of plastics were successfully identified despite their similar chemical structure.