Two samples of composition La0.9M0.1CoO3 (M = Sr, Ce) have been compared as catalysts for the flameless combustion of methane. The former showed a lower activity than the latter and this difference was enhanced at lower temperature. Aiming at understanding the origin of this behaviour, EPR analysis was carried out at temperatures down to 100 K. At T < 245 K a zero-field intense feature appeared with the M = Sr sample only, characterized by opposite phase with respect to the g approximately 2 line. This zero-field line was attributed to microwave absorption by spin glass formed by cobalt- and oxygen-based paramagnetic ions. The tendency to strong interaction among these species could also be a reason of the low oxygen availability for the catalytic methane oxidation at higher temperature.