The invention discloses a multi-layer ionic membrane composite electrode vanadium battery, and belongs to the field of vanadium batteries. The multi-layer ionic membrane composite electrode vanadium battery disclosed by the invention comprises an electrolyte solution and an ionic membrane arranged inside the electrolyte solution, wherein electrodes are arranged on two sides of the ionic membrane respectively, and the bottoms of the electrodes are inserted in the electrolyte solution; the ionic membrane is a multi-layer material and is a V(III)/V(IV) sulfuric acid solution system mixed electrolyte solution containing an additive, and the electrodes are graphene composite electrodes. The multi-layer ionic membrane composite electrode vanadium battery disclosed by the invention has the characteristics of relatively low vanadium ion crystallization ratio, relatively low vanadium ion permeability, long service lifetime, safety and stability in use.