Provided is a method of forming an insulating film on a substrate by using atomic layer deposition (ALD). The method of forming an insulating film on a substrate by using ALD includes transferring a deposition-hindering material to the substrate, and depositing a first material layer by transferring a first precursor to the deposition-hindering material, wherein the deposition-hindering material includes an organic ligand, and the first precursor includes an alkoxide ligand.