Existing online monitoring system for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), technically named Thermal Desorption-Gas Chromatography-Tunable Laser Ionization-Time of Flight Mass Spectrometry (TD-GC-TLI-TOFMS), has been applied in several incinerators in China. TD-GC-TLI-TOFMS can realize rapid detection of PCDD/Fs emissions from incineration sources. However, the long-term measurement of unclean flue gas will pollute the instruments in TD-GC-TLI-TOFMS, and interfere with the peak output of the target 1,2,4-trichlorobenzene (1,2,4-TrCBz). In this study, Deans switch (DS) was utilized for the first time in an online monitoring system for PCDD/Fs to separate 1,2,4-TrCBz signal from impurity signals, which improved the anti-interference capability of the system. Laboratory standard gas experiments showed that after adding a DS device between GC and TLI pulse valve, when the pressure set in DS was 4 psi and switched before or near the peak output of 1,2,4-TrCBz, the change of 1,2,4-TrCBz signal intensity was minimal. The impurities near the target peak were removed, and TLI-TOFMS was highly stable during continuous measurement. Moreover, the maximum intensity peak time of 1,2,4-TrCBz was stable after using DS in different switching time intervals. When connecting DS to TD-GC-TLI-TOFMS for field validation on the tail flue gas of a municipal solid waste incinerator (MSWI), results showed that a better 1,2,4-TrCBz signal could be obtained with a 69.52 % reduction of impurity peaks at the moments closer to the target peak. Furthermore, DS improved the sensitivity of the system to low concentration variations of 1,2,4-TrCBz in the flue gas. The robust system developed in this study can be better applied to incineration factories with poor combustion or suboptimal purification technology, facilitating online PCDD/Fs monitoring.