Cosmetic compositions capable of forming a multilayer structure after application to a keratinous material are provided, as well as methods of applying such compositions to keratinous material. Certain compositions comprise: Component A which comprises about 0.01% to 50% by weight with respect to the total weight of the composition of at least one silicone- and/or hydrocarbon-containing film forming agent having at least one glass transition temperature which is lower than 60° C.; Component B which comprises about 0.01% to 90% by weight with respect to the total weight of the composition of one or more silicone compounds having a viscosity of greater than about 10 million cSt; and an inorganic pigment, skin active agent, skin adjuvant, or UV filter; wherein the weight ratio of the silicone- and/or hydrocarbon-containing film forming agent(s) in Component A to silicone compound(s) in Component B of about 1:1.5 to about 1:100.