The invention relates to a preparation method of a carbon dioxide responded graphene nano hybrid material, which comprises the following steps of reacting 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphine with 1,1-dimethoxy-N,N-dimethylethylamine so as to obtain 5,10,15,20-tetrakis(4-phenyl-N,N-dimethyl-N''-acetamidine bicarbonate)-21H,23H-porphine; and then, adding grapheme, so that molecules of the 5,10,15,20-tetrakis(4-phenyl-N,N-dimethyl-N''-acetamidine bicarbonate)-21H,23H-porphine are coupled on the surface of the grapheme, and then a grapheme-5,10,15,20-tetrakis(4-phenyl-N,N-dimethyl-N''-acetamidine bicarbonate)-21H,23H-porphine nano hybrid material is formed. The grapheme hybrid material prepared according to the invention has carbon dioxide responsiveness, and the dispersion of the hybrid material in an aqueous solution can be reversibly regulated through feeding carbon dioxide or argon into the aqueous solution, and therefore, the hybrid material has wide applications in the fields of drug controlled release carriers, intelligent switches, intelligent sensors, biological nano-devices and the like. The preparation method disclosed by the invention is simple and practicable, and raw materials can be subjected to industrialized production, and therefore, the preparation method has good popularization and application values.