In conclusion, this work presents a strategy integrating MciroED with combinatorial chemistry to synthesize extra-large pore zeolite and accelerate purification process optimization. The resulting zeolites, NJU120-1 and NJU120-2, featuring 22MR extra-large pores and tailored nano morphologies, demonstrated exceptional catalytic performance exceeding that of commercial benchmarks. Extra-large-pore zeolites hold great promise for catalysis of bulky molecules but remain difficult to design, synthesize, and scale. Current challenges include the empirical nature of structure-directing agents, limited high-throughput characterization, framework stability under harsh conditions, and high production costs. Future advances will rely on seeds-assisted crystallization, novel directing agents, and integrated characterization approaches, enabling broader structural diversity and practical catalytic applications.