Highlights ► Lipase was entrapped in zirconia particles by bio-mineralization of K2ZrF6. ► Zirconia particles with or without lipase owned good spherical structure of 150nm. ► The entrapped lipase showed improved thermal, pH, recycling and storage stabilities. ► The resolution of (R,S)-1-phenylethanol could be catalyzed by the entrapped lipase. ► Entrapping enzyme in zirconia induced by protamine is good for enzyme immobilization.