A series of Mn containing layered double hydroxides (Mn/Mg/Al-LDH) were prepared by co-precipitation method, and their catalytic behavior on the removal of toluene via Mn/Mg/Al-LDH based low-temperature plasma synergistic catalysis was investigated. XRD and FT-IR were used to characterize the structure of the Mn/Mg/Al-LDH. The results showed that Mn/Mg/Al-LDH had a typical LDH layered structure. The catalytic behavior on removal of toluene reached higher than 90% under a specific SIE value. Catalyst characterization showed that active ingredients of MnOx were formed on the surface of the catalyst and the catalyst had higher oxidation activity on removal of toluene, and the activity weakened after high temperature calcination.