The invention relates to a rechargeable aluminum air battery based on sunlight assistance and a preparation method thereof. According to the technical scheme, the method comprises the following steps: preparing an air photoelectrode: preparing a mixed solution of potassium iodide and bismuth nitrate pentahydrate, adjusting the pH value by using dilute nitric acid, dropwise adding a prepared p-benzoquinone ethanol solution into the solution, stirring, depositing BiOI on conductive glass by using an electro-deposition method, performing washing, and performing airing; finally, dropwise adding a dimethyl sulfoxide solution of vanadyl acetylacetonate onto BiOI, calcining, performing cooling to room temperature, immersing into a NaOH solution, washing with deionized water, and performing natural airing to obtain the BiVO4 photoelectrode. The material with excellent photocatalytic activity and stability is prepared, and the charging voltage can be greatly reduced by introducing sunlight. According to the invention, collaborative conversion of solar energy, chemical energy and electric energy is realized, and a new way is opened up for the rechargeable aluminum air battery.