Disclosed are multilayer protective materials used to make clothes for firemen and rescue workers operating in areas of high temperature and open flames. These materials can be used to manufacture articles such as capes, covers and blankets which must show increased heat resistance and are used for operation in areas of intense heat radiation and open flames during fire suppression, including burning sources of oil, gas and other substances. The object of the invention includes: a heat insulating material comprising a heat-resistant fiber substrate; a layer of waterproof material with a metal coating, said layer consisting of a cross-linked polymer having a liquid diffusion coefficient equal or less than 10 g * sec/cm ; and a hermetic layer made of a rubber-based elastomer. Alternatively, the layer of waterproof material is made of a porous material selected from a group comprising polyolefins and fluorine-, chlorine- or silicon-containing polymers; whereby the size of the pores is between 0,01 and 1,0 micrometers. The layer of metal coating is an aluminum, copper or titanium nitride layer having a thickness of between 0,05 and 0,25 micrometers. The invention allows said materials to be used in order to sew more comfortable protective clothes which permit direct discharge of body vapors through the heat insulating material, have better fireproof features due to a better resistance to open flames, ensure the resistance of material as long as the heat effects last and provide for a longer life span of the said clothes; moreover, they permit to simplify the structure of the set of materials used to make the clothes and improve their operating properties as well as increasing the effectiveness of the protective action thereof.