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Disclosed here is a method for making a monolithic rare earth oxide (REO) aerogel, comprising : preparing a reaction mixture comprising at least one rare earth metal nitrate, at least one epoxide, at least one base catalyst, and at least one organic solvent; curing the mixture to produce a wet gel; drying the wet gel to produce a dry gel; and thermally annealing the dry gel to produce the monolithic REO aerogel. Also disclosed is an REO aerogel comprising a network of REO nanostructures, wherein the REO aerogel is a monolith having at least one lateral dimension of at least 1 cm, wherein the REO aerogel has a density of about 40-500 mg/cm3 and/or a BET surface area of at least about 20 m2/g, and wherein the REO aerogel is substantially free of oxychloride.