ability. Here we report a novel, highly stable pure silica zeolite, ZEO-3, with a multidimensional, interconnected system of extra-large pores open through windows made by 16 and 14 SiO4 tetrahedra, which is the less dense polymorph of silica known so far. With a specific surface area over 1000 m 2 /g, ZEO-3 shows an extraordinary performance for Volatile Organic Compounds abatement and recovery. This zeolite is formed by a 1D-to-3D topotactic condensation of a chain 5 silicate, an unprecedented, never predicted approach.