Monolithic macroporous barium zirconate has been successfully prepared via a sol–gel process accompanied by a phase separation route. The amount of polyoxyethylene (PEO) and propyleneoxide (PO) control the morphology and structure of the monolithic macroporous barium zirconate. The xerogel has a high porosity reaching 63% and a large BET surface area reaching 188 m2∙g−1.