The invention relates to a polyimide fiber spinning solution based on 2, 2-double [4-(2, 4-diaminophenoxy) phenyl group] hexafluoropropane and a preparation method thereof. The structural formula of components of the spinning solution is shown as below. The preparation method includes adding the 2, 2-double [4-(2, 4-diaminophenoxy) phenyl group] hexafluoropropane and a high-polar aprotic organic solvent into a reaction kettle, stirring for dissolution at the room temperature, adding phthalic anhydride, stirring for reaction for half an hour, cooling until the temperature is under 5 DEG C through an ice-water bath, adding 3, 3', 4, 4'-tetracarboxy benzophenone dianhydride, stirring for reaction for half an hour, adding pyromellitic dianhydride, maintaining the reaction temperature under 5 DEG C, and obtaining the solution after stirring for reaction for 2-4 hours. The polyimide fiber spinning solution based on the 2, 2-double [4-(2, 4-diaminophenoxy) phenyl group] hexafluoropropane and the preparation method thereof have the advantages that molecular weight of resin is easy to control, molecular structure is easy to regulate, preparation of high-performance polyimide fibers is facilitated, reaction condition of the preparation method is mild, and industrialization of products is facilitated.