Size-exclusion chromatography (SEC) is often used to determine the molecular weights of and separate polymers and proteins. The porous packing of the SEC column effects the separation of molecules, with larger molecules eluting earlier. Interest in high-speed SEC for larger molecules has been building, especially for combinatorial polymerization reactions and online SEC-MS applications. Mechanical stability of the packing, which siliceous materials have more of than polymeric ones, therefore needs to be improved. Several silicas have been explored but limited pore sizes and pore volumes have restricted their usage to separating small molecules. Siliceous MCF templated using oil-in-water microemulsions has good potential for SEC packing because it has ultralarge pore size (20-50 nm), high porosity and sturdy skeleton. However conventional MCF consists of highly irregular particles and hence cannot be used as packing.