Syngas can be efficiently converted to multimethylbenzenes by integrating a methanol synthesis catalyst with HZSM-5 zeolites, where 1,2,4,5-tetramethylbenzene (durene) is a high value-added product used in polyimide synthesis. Here, we synthesized a Mn modified ZnAlO_x catalyst with petaloid structure and integrated with HZSM-5 as a bifunctional catalyst for targeting the high selectivity durene. Various characterization approaches including XRD, BET, XPS, SEM, TEM, TPD, TPR, and in-situ FTIR were adopted to illustrate the deeper analysis of highly efficient catalyst. It was demonstrated that the strong synergy of ZnAlO_x staggered sheet and nanoclusters MnO_x caused higher concentration of H₃CO* species and methanol/DME intermediates, which promote the methylation of trimethylbenzene over HZSM-5 zeolites. The combination 7%Mn-ZnAlO_x/ HZSM-5 exhibited a high CO conversion of 56.4% and 44.6% tetramethylbenzene selectivity at 360 ℃ and 5.0 MPa, with an excellent stability of 100 h. In addition, through trace methanol co-feeding experiment, it was proposed that there is an appropriate amount of methyl intermediates to match with the synthesized zeolite to obtain a maximum selectivity to tetramethylbenzene.