Michael reaction of β-ketoesters with vinylketones at room temperature under solvent-free condition is investigated with various Fe3+ catalysts, including FeCl3⋅ 6H2O supported on various supports (Fe–mica, Fe–mont, Fe–SiO2, Fe–Al2O3, Fe–NaY) and homogeneous catalysts, FeCl3⋅ 6H2O and Fe (NO3) 3⋅ 9H2O. Fe3+-exchanged fluorotetrasilicic mica (Fe– mica) shows highest activity. Fe–mica exhibits almost quantitative yields of Michael ...