The ruthenium(II) 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin carbonyl complex has been covalently attached to a 3-aminoporpyl functionalized silica gel. This supported complex is found to efficiently catalyze the epoxidation of the Delta(5)-unsaturated steroid derivatives with high conversion, epoxide yield and P-selectivity. High P-selectivity is also observed for the epoxidation of a Delta(4)-unsaturated steroid though the conversion and derivative are low. This new silica-supported polyhalogenated metalloporphrin catalyst can be easily recovered after reaction and has shown high stability over repeated uses. No catalyst leaching is detected in these reactions. (c) 2005 Elsevier B.V. All rights reserved.