A novel synthetic route to a series of cerium bromide solvates is reported. The combination of bulk cerium bromide and the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide results in a precursor paste that enhances the solubility of the cerium(III)bromide moiety in a number of donor solvents. Crystallization from these solvents has resulted in the isolation and characterization of CeBr3(THF)(4) (2), CeBr3(2-Me-THF)(4) (3), and CeBr3- (MeCN)(5) center dot MeCN (4). Additionally, 2 is shown to be an efficient precursor for the new species CeBr3(py)(4) (5) and CeBr3(bipy)(py)(3) (6).