Pigmented cosmetic compositions capable of forming a multilayer structure after application to a keratinous material are provided, as well as methods of using same. Certain compositions comprise (a) Component A which comprises (i) about 0.01% to 60% 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 normal human body temperature; (ii) at least one pigment or filler, wherein the pigment or filler is surface-treated with a trialkoxyalkylsilane; and (b) Component B which comprises (i) about 0.01% to 90% by weight with respect to the total weight of the composition of one or more silicone compounds in amounts sufficient to achieve a viscosity of about 1,000 cSt to 10,000,000 cSt; wherein the Component A and Component B are immiscible.