The invention relates to a method for preparation of hexanolactam with 5-formoxyl methyl valerate. In the method, 5-formoxyl methyl valerate, ammonia and hydrogen are used as raw materials and the hexanolactam is prepared in a reactor lined with polyfluortetraethylene under the condition with a supported metal catalyst; the reaction temperature is 353-473K; the reaction pressure is 0.5-10.0MPa; the catalyst consists of a carrier and a metal component, wherein the carrier is alumina, silica, zirconia, zinc oxide, titanium dioxide or activated carbon, and the metal component is a VIII group metal and accounts for 0.01-20.0 percent of the total weight of the catalyst.