BACKGROUND: The formation of polyphenol microspheres by the polymerization of 3-methylcatechol was performed in a methanol/phosphate buffer solution using horseradish peroxidase (HRP), without the use of a surfactant or a water/oil interface, to be used for germanium recovery. RESULTS: The polyphenol microspheres were of diameter 1 mm. The functional group density of phenol group in the polymer was approximately 15mol kg(-1) determined by the Folin-Denis method. In batchwise experiments, the amount of germanium adsorbed was 0.23mol kg(-1). CONCLUSION: Because germanium is a rare metal, a system for its recovery is required. Using the proposed system, continuous recovery of germanium can be achieved using multilayered microspheres. (C) 2011 Society of Chemical Industry