The rapid and massive accumulation of greenhouse gas CO2 in the atmosphere directly leads to global warming, ecological damage, and other environmental problems. From the perspective of renewable carbon resource utilization, CO2 is a widespread, inexpensive, and easily available C1 resource. The synthesis of ethylene carbonate employing CO2 as raw material provides a feasible industrial scheme for CO2 utilization with the atomic economy. The traditional efficient catalyst for this cycloaddition is halogen ionic liquid. However, the loss of halogen ions in the cycloaddition process leads to the additional consumption of epoxide and the generation of halogenated alcohol, thus decreasing the selectivity and yield of the main product, resulting in separation difficulty and improving equipment requirements. Therefore, it is necessary to develop an ideal catalytic system to inhibit and transform the by-product of halogenated alcohols. In this work, a series of alkalescent ionic liquids had been designed and developed to realize the in?situ conversion of bromoethanol under the condition of cycloaddition (temperature of 130℃, CO2 pressure of 3 MPa, reaction time of 3 h). The effects of different reaction conditions and different alkaline ionic liquids on the conversion of bromoethanol were investigated, including ionic liquid type, reaction temperature, different pressure environment, reaction time, etc. The reaction law of bromoethanol conversion was revealed, among which [Bu4P][HCO3] showed optimal performance. Using gas atmosphere and solvent microenvironment to regulate different reaction paths, the conversion rate of bromoethanol reached 20%~50%. After ethylene carbonate (EC) addition, the by-products with bromine-containing covalent bonds were reduced, which was more conducive to the formation of bromine ions. The conversion of halogen covalent bonds to halogen ions restored part of the catalytic activity of the cycloaddition reaction system. This was a simple versatile approach, which can realize the in?situ regulation of bromoethanol conversion pathways in the CO2 cycloaddition system, and promote the optimization of the CO2 utilization system and the circulation of halogen ions, hence possessing important scientific significance and application value.