The invention belongs to the field of petroleum engineering and relates to a shale gas reservoir pre-fracture composite acid solution and its preparation method and application. The composite acid solution comprises the following components: Component a) at least one component of hydrochloric acid, hydrofluoric acid, fluorboric acid, phosphoric acid, formic acid and acetic acid; and Component b) a corrosion inhibitor, a discharge aiding agent, a ferric iron stabilizer and a clay stabilizer. The composite acid solution containing different acids is selected for different reservoirs. Rock core corrosion ratio is 25-30%. A certain rock core corrosion ratio is maintained, and borehole wall collapse caused by too high corrosion ratio is also prevented. The corrosion inhibitor, the discharge aiding agent, the ferric iron stabilizer and the clay stabilizer which are used as additives have good compatibility with acid. The composite acid solution provided by the invention has advantages of fast dissolving speed, uniform mixing, high corrosion inhibition efficiency, high surface activity, good clay stabilizing effect and wide range. Applicable temperature of the composite acid solution is 20-180 DEG C. by the use of the composite acid solution, normal construction of large-scale fracturing of long horizontal-section shale gas wells can be guaranteed under the condition of existing equipment capacity.