This study demonstrates the applicability of laser mass spectrometry for safety management of the processed gas and the work environment in a polychlorinated biphenyl (PCB) disposal plant. By utilization of laser ionization/ion trapping storage/time-of-flight mass spectrometry (LI-IT-TOFMS), we analyzed gaseous PCBs from scrap capacitors with on-line detection. It was confirmed that few contaminants were detected in the spectrum. By the effect of laser-induced selective ionization, it was considered that there was little interference with the mass range of PCBs. The accuracy of LI-IT-TOFMS when analyzing environmental gas was almost the same as that for the PCB standard gas. It was possible to perform on-line analysis of the work environment for over 2000 h (120 000 data points). LI-IT-TOFMS was thus shown to be a very useful method for ensuring the safety of the work environment in disposal plants for PCBs.