Value-added aromatics are very important building-block chemicals for the production of plastics, polymers, solvents, pesticides, dyes, and adhesives. COx conversions to aromatics (CTA) are very promising approaches for the synthesis of aromatic monomers, which are catalyzed via bifunctional catalysts in a single reactor. The methanol/dimethyl ether and/or olefins intermediates formed from hydrogenation of COx on metal components can be converted into aromatic monomers exclusively on the zeolite by cascade reactions. To realize the cascade reaction, Fischer–Tropsch synthesis (FTS) reaction on the hybrid catalysts containing a highly ordered mesoporous FeZrOx bimetal oxide physically mixed with Mo-modified ferrierite (Mo/HFER) were carried out to directly produce environmentally benign middle distillates and aromatics (BTXs) from syngas. Promoter effects of Mo species impregnated on HFER was investigated, at an optimal Mo content (~6 wt%) on the HFER frameworks. The hybrid FeZr-Mo(6)/HFER showed the synergistic effects such as higher CO conversion to liquid hydrocarbons for C5–C20 including aromatics with a smaller CO2 formation due to the less accumulation of carbonaceous deposits, optimum hydrophilicity, lower water-gas shift (WGS) reaction activity and larger number of weak acid sites. However, an excessive amount of Mo promoter (> 6 wt%) on the acidic HFER surfaces accelerated the formation of the graphitic carbons leading to the decrease of catalytic activity, which were attributed to its excess hydrophobicity and small amounts of acidic sites. The efficient production of aromatics with controllable aromatics distributions still remain a great challenge, and the direct CO2 hydrogenations to high aromatics have received considerable attention. Consequently, the ZSM-5 zeolite having different morphologies such as nano-structured (N-ZSM5), hierarchically hexagonal nano-structured (H-ZSM5), sheet-like (S-ZSM5) and conventional sphere-type (C-ZSM5) structures exhibited varied catalytic activity, formation of aromatics, and their product distribution and deactivation behaviors. The larger number of strong Brønsted acid sites on the bifunctional ZnZrOx/N-ZSM5 due to the smaller crystallite size of ZSM-5 was responsible for a higher CO2 conversion of 18.7% and aromatics selectivity of 70.8%. The lager amount of external Brønsted acid sites on the H-ZSM-5 revealed a higher selectivity to bulky tetramethyl benzene (TMB) with 88.2% due to an enhanced surface C-C coupling reaction formed by stepwise hydrogenation of CO2. The morphologies of ZSM-5 on the bifunctional ZnZrOx/ZSM-5 revealed larger impacts for CO2 conversion on the ZnZrOx metal oxide as well as aromatics distributions Among the synthesized aromatics especially BTX (benzene, toluene and xylenes) and in particular, para-Xylene (PX) is an essential raw chemical for valuable products. Considerably, PX is generated inside the pores of ZSM-5 zeolite and undergoes concurrent alkylation to form heavy aromatics or isomerization to other isomers on the external surface Brønsted acid sites during the diffusion process. Consequently, the selectivity of BTX and PX can be enhanced by eliminating the external Brønsted acidity of ZSM-5 through the passivation process. Therein, we encapsulated the HZSM-5 with non-acidic Silicalite-1 shell (HZSM-5@S1) to stop the further isomerization and alkylation of formed BTX. Consequently, the HZSM-5@S1 hyderdized with Fe/ZnZrOx catalyst enhanced the fractions of BTX in aromatics and total hydrocarbon products from 20.1% and 14.4% to 78.5% and 54.6%, respectively.