A system and method for performing laser induced breakdown spectroscopy during laser ablation of a coating, such as a TBC coating, deposited on a surface of a component, particularly to enable obtained spectrometry signals of the ablated coating to be used to monitor and control the laser ablation removal process in real-time. The system includes a laser energy source and a scan head interconnected with the laser energy source to receive a laser beam therefrom and then direct the laser beam onto the surface of the coated component. Collection optics collect radiation emitted from a laser-induced plasma generated by the laser beam at the surface of the coated component. The system is further equipped to spectrally analyze the radiation and generate a feedback signal for control and optimization of one or more operational parameters of the laser energy source in real-time.