The invention discloses a preparation method of a graphene/stannic oxide composite nanofiber membrane and an application, and relates to anode materials for lithium-ion batteries. The preparation method comprises the following steps: adding graphene to deionized water and carrying out ultrasonic treatment; adding NaOH and stannic chloride under a stirring condition, and mixing the deionized water evenly to obtain a mixed solution; transferring the mixed solution to a reaction kettle for reaction, and filtering, cleaning and drying the mixed solution to obtain graphene/stannic oxide composite nano-particles; ultrasonically dispersing the graphene/stannic oxide composite nano-particles into a mixed solvent of methanol and water, and adding PVAc to obtain a spinning precursor solution; carrying out high-pressure electrospinning on the spinning precursor solution to obtain a PVAc/graphene/stannic oxide composite nanofiber membrane; and carrying out drying and thermal treatment to obtain the porous graphene/stannic oxide composite nanofiber membrane, wherein the diameters of fibers in the composite nanofiber membrane are 800-1200nm and the lengths are greater than 0.5mm. A conductive agent and a binder do not need to add, and the graphene/stannic oxide composite nanofiber membrane can be directly applied to preparation of the lithium-ion battery as an electrode material.