Laser-induced plasma emission spectrometry has been applied to the analysis of poly(vinyl chloride) materials. Methodologies used to optimize the monitoring of the time-dependent emission from the laser-induced plasma are discussed, and the effects of key parameters, such as laser energy, sample position and repetitive firing at given sites, were examined. Basic performance data are reported for Ca [limit of detection 0.016% m/m and 4.8% relative standard deviation (RSD)] and Sb (limit of detection 0.04% m/m and 4.8% RSD) and the potential use for rapid survey analysis is demonstrated.