A method and system for monitoring laser shock peening of a work piece. A line spectrum is obtained from radiation emitted by a plasma produced by a laser shock peening process. The shape of the line spectrum about its emission peak is compared to a defined line shape to verify proper operation of the laser shock peening process. The line shape may be a Lorentzian line shape corresponding to a desired line shape. The line shape may a Gaussian line shape corresponding to an undesired line shape. The system can also detect the failure mode that occurs when the opaque layer is broken through by detecting the plasma spectral component produced by the work piece material, along with the plasma produced by the opaque layer.