Thermochemical splitting of carbon dioxide to carbon-containing fuels or value-added chemicals is a promising method to reduce greenhouse effects. In this study, we propose a novel process for synchronous promotion of chemical looping-based CO 2 splitting with biomass cascade utilization. The superiority of the process is reflected in (1) a biomass fast pyrolysis process is carried out for syngas, phenolic-rich bio-oil, and biochar co-production with oxygen carrier reduction; (2) the reduced oxygen carrier and the biomass-derived biochar were both applied for CO 2 splitting during the oxygen carrier oxidation stage with carbon monoxide production as well as oxygen carrier re-oxidation; (3) the redox looping of the oxygen carrier was found to synchronously promote the comprehensive utilization of biomass and CO 2 splitting to CO. Various characterizations e.g. HRTEM- and SEM-EDX mapping, H 2 -TPR, CO 2 -TPO, XRD, XPS, N 2 nitrogen adsorption and desorption isotherm tests, Mössbauer, etc. were employed to elucidate the aerogels' microstructures, phase compositions, redox activity, and cyclic stability. Results indicate that the Ca 2 Fe 2 O 5 aerogel is a promising initiator of the proposed chemical looping process from the perspectives of biomass utilization efficiency, redox activity, and cyclic durability.