Large-pore cubic (Im3m) mesoporous silica single crystals have been synthesized by using commercial nonionic block copolymers as templates and inorganic salts as additives. These single crystals possess exclusively uniform rhombdodecahedron shapes ( approximately 1 mum) with approximately 100% yield. The mesopore lattice array in each crystal face is solved by TEM, further confirming that these crystals are perfect single crystals.