Carbonic anhydrase (CA) as a typical metalloenzyme in biological system can accelerate the hydration/dehydration of carbon dioxide (CO2, the major components of greenhouse gases), which performer with high selectivity, environmental friendliness and superior efficiency. However, the free form of CA is quite expensive (-RMB 3000/100 mg), unstable, and non-reusable as the free form of CA is not easy for recovery from the reaction environment, which severely limits its large-scale industrial applications. The immobilization may solve these problems at the same time. In this context, many efforts have been devoted to improving the chemical and thermal stabilities of CA through immobilization strategy. Very recently, a wide range of available inorganic, organic and hybrid compounds have been explored as carrier materials for CA immobilization, which could not only improve the tolerance of CA in hazardous environments, but also improve the efficiency and recovery to reduce the cost of large-scale application of CA. Several excellent reviews about immobilization methods and application potential of CA have been published. By contrast, in our review, we stressed on the way to better retain the biocatalytic activity of immobilized CA system based on different carrier materials and to solve the problems facing in practical operations well. The concluding remarks are presented with a perspective on constructing efficient CO2 conversion systems through rational combining CA and advanced carrier materials. (C) 2020 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.