The crystallization of barium oxalate in the presence of a double-hydrophilic block copolymer poly(ethylene glycol)-block-poly(methacrylic acid) (PEG-b-PMAA) was investigated. Barium oxalate crystals with a complex form, such as fan-like aggregates consisting of rod-like BaC 2O 4·H 2O crystals and spherical aggregates consisting of flake-like BaC 2O 4·3.5H 2O crystals were readily produced in aqueous solutions of PEG-b-PMMA. This result may provide an effective method for controlling the morphology and polymorph of inorganic crystals.