Ca 2 FeAl 1Àx Mg x O 5 (x ¼ 0, 0.05 and 0.1) compounds adopting the brownmillerite-type structure were prepared by a self-combustion route using two different fuels. Characterisation was performed using X-ray powder diffraction, Mo¨ssbauer spectroscopy, magnetisation measurements, chemical analysis, scanning electron microscopy and 4-point dc conductivity measurements. Global results indicate that the solubility limit was reached for x ¼ 0.1. An antiferromagnetic behaviour was detected for all studied compositions, with magnetic ordering temperatures of 340 and 290 K for x ¼ 0 and 0.05, respectively. Mg doping increases the number of iron cations in tetrahedral sites, which induces magnetisation enhancement at low temperatures through the coupling between octahedral iron cations in different octahedral planes. The compounds exhibit semiconductor behaviour and Mg 2+ doping yields a significant enhancement of the total conductivity, which can be essentially attributed to the presence of Fe 4+ ions. r