The selectivity limitation has long posed a significant challenge in the conversion of CO or CO2 into liquid hydrocarbon-based sustainable fuels via Fischer–Tropsch synthesis (FTS) and other related processing pathways due to the Anderson–Schulz–Flory (ASF) distribution. The unique pore structure, thermal stability, and acidic sites of ZSM-5 have enabled its widespread applications in various catalytic processes of value-added chemicals and sustainable fuels. In the reaction pathways from CO/CO2 to liquid HCs of interest, incorporating ZSM-5 into metal catalysts provides new opportunities to enhance product selectivity and catalytic activity, and even lower the reaction energetics. This review highlights recent advancements over the past five years in the structural design of ZSM-5-based catalysts aimed at improving the conversion selectivity of advanced liquid biofuels such as renewable diesel and sustainable aviation fuel. It explores innovative strategies for optimizing catalyst composition, the acidity, mesoporosity, and structures of ZSM-5 to design more efficient, selective, and robust catalysts. Additionally, the review addresses the direct hydrogenation of CO and CO2 into C5+ liquid hydrocarbons, focusing on catalyst selection, acidic site optimization, and the structural configuration of ZSM-5. The mechanisms involved in these processes are also surveyed.