Suppression of tritium permeation through structural materials is essential in order to mitigate fuel loss and radioactivity concerns. Ceramic coatings have been investigated for over three decades as tritium permeation barriers (TPBs); however, a very limited number of investigations on the mechanism of hydrogen-isotope permeation through the coatings have been reported. In this study, deuterium permeation behaviour of erbium oxide coatings fabricated by filtered arc deposition on reduced activation ferritic/martensitic steels has been investigated. The samples coated on both sides of the substrates showed remarkably lower permeability than those coated on one side, and the maximum reduction efficiency indicated a factor of 105 compared with the substrate. The different permeation behaviour between the coatings facing the high and low deuterium pressure sides has been found by the crystal structure analysis and the evaluation of the energy barriers. It is suggested that the permeation processes on the front and back surfaces are independent, and the TPB efficiency of the samples coated on both sides can be expressed by a multiplication of that of each side.