The present study examines the applicability of two iron-containing perovskites, LaFeO3 (LFO) and BiFeO3 (BFO), as nanocatalysts for heterogeneous Fenton-like reactions using phenol and methyl tert-butyl ether (MTBE) as model contaminants. LFO and BFO synthesized according to a sol-gel method using citric acid as complexing agent have a crystallite size of about 60-70 nm with specific surface areas of 5.2 m(2) g(-1) for LFO and 3.2 m(2) g(-1) for BFO. In heterogeneous Fenton-like reactions, LFO and BFO showed similar pseudo-first order rate constants for phenol oxidation (k(LFO)' = (0.13 +/- 0.01) h(-1) and k(BFO)' = (0.15 +/- 0.01) h(-1)) at pH = 7 when 0.1 g L-1 catalyst and 3.0 g L-1 H2O2 were applied. Degradation efficiency was improved for both perovskites by a factor of approximately three when the pH value was slightly decreased to pH = 5. An increase of the reaction temperature from 20 degrees C to 60 degrees C during the BFO-catalyzed reaction led to a significant acceleration of phenol removal of about one order of magnitude (k(BFO)' = (1.9 +/- 0.1) h(-1)). High stability and reusability of the BFO particles was confirmed in four successive oxidation batches using MTBE as model contaminant. In addition, the mechanism of the perovskite-catalyzed Fenton-like system was studied by applying compound-specific stable isotope analysis (CSIA). The perovskite-catalyzed oxidation appears to follow a pathway similar to that of the homogeneous Fenton reaction, Le. center dot OH radicals play a dominant role as primary reactive species. (C) 2013 Elsevier B.V. All rights reserved.