A large amount of zeolite structures are still not synthetically available or not available in the form of aluminosilicate currently. Despite significant progress in the development of predictive concepts for zeolite synthesis, accessing some of these new materials is still challenging. One example is the IWR structure as well. Despite successful synthesis of Ge-based IWR zeolites, direct synthesis of aluminosilicate IWR zeolite is still not successful. In this report we show how a suitable organic structure directing agent (OSDA), through modeling of an OSDA/zeolite cage interaction, could access directly the aluminum-containing IWR structure (denoted as COE-6), which might allow access to new classes of materials and thus open opportunities in valuable chemical applications. The experimental results reveal that the COE-6 zeolites with a SiO2/Al2O3 ratio as low as 30 could be obtained. Very interestingly, the COE-6 zeolite has much higher hydrothermal and thermal stabilities than those of the conventional Ge-Al-IWR zeolite. In methanol-to-propylene (MTP) reaction, the COE-6 zeolite exhibits excellent selectivity for propylene, offering a potential catalyst for MTP reaction in the future.