The invention relates to a novel polytetrafluoroethene (PTEF) nanocrystallization material and a preparation method thereof. According to the preparation method for the novel material, functional multiwalled carbon nanotube (MENT) thin films are self-assembled on PTEF substrates layer by layer. The invention also provides a novel PTEF nanocrystallization artificial blood vessel and a preparation method thereof. The preparation method has the advantages that the MENT thin films are self-assembled on the PTEF substrates which are pre-treated by phthalic diglycol diacrylate (PDDA), so that the performance of the substrate materials can be improved well by the simple and convenient preparation method, and the MENT thin films which are self-assembled layer by layer by taking PTEF as the substrates can be widely applied; and the MENTs can be combined with PTEF blood vessel materials which are clinically used on large scale at present, the degree of intimal hyperplasia of the blood vessels, which is caused after implantation of artificial blood vessels can be reduced, the patency rate of the blood vessels is improved, and a feasible method is provided for improving the curative effect of the implantation operation of the artificial blood vessels clinically.