The invention provides a covalent organic framework material with respiratory effect, and a preparation method and an application thereof, the covalent organic framework material with respiratory effect is formed by condensation of a flexible construction unit TFMB and rigid TAPM aldehydeamine, and the covalent organic framework material has high stability, can keep stable for several months in the use process, is basically free of decomposition phenomenon, can be recycled, has a breathing effect, can be subjected to structural transformation after completely drying and adsorbing solvent gas molecules, has a closed pore state and an open pore state, is in a closed pore state when completely drying, can be subjected to structural change after adsorbing the solvent gas molecules, and is reversible; the material has good potential in the aspects of gas adsorption and separation, has good application prospect in the field of intelligent response materials, and has a structural formula shown in the specification, in the formula, R is selected from H, Ph, NO2, SH, F, Br and SO3H;.