Reverse water–gas shift chemical looping (RWGS-CL) offers a promising means of converting the greenhouse gas of CO2 to CO because of its relatively low operating temperatures and high CO selectivity without any side product. This paper introduces a core–shell structured oxygen carrier for RWGS-CL. The prepared oxygen carrier consists of a metal oxide core and perovskite shell, which was confirmed by inductively coupled plasma mass spectroscopy (ICP-MS), XPS, and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) measurements. The perovskite-structured shell of the prepared oxygen carrier facilitates the formation and consumption of oxygen defects in the metal oxide core during H2-CO2 redox looping cycles. As a result, amounts of CO produced per unit weight of the core–shell structured oxygen carriers were higher than that of a simple perovskite oxygen carrier. Of the metal oxide cores tested, CeO2, NiO, Co3O4, and Co3O4-NiO, La0.75Sr0.25FeO3-encapsulated Co3O4-NiO was found to be the most promising oxygen carrier for RWGS-CL, because it was most productive in terms of CO production and exhibited long-term stability.