A photoresist composition and methods using the photoresist composition in multiple exposure/multiple layer processes. The photoresist composition includes a polymer comprising repeat units having a hydroxyl moiety; a photoacid generator; and a solvent. The polymer when formed on a substrate is substantially insoluble to the solvent after heating to a temperature of about 150° C. or greater. One method includes forming a first photoresist layer on a substrate, patternwise exposing the first photoresist layer, forming a second non photoresist layer on the substrate and patterned first photoresist layer. Another method includes forming a first photoresist layer on a substrate, patternwise exposing the first photoresist layer, forming a second photoresist layer on the substrate and patterned first photoresist layer and patternwise exposing the second photoresist layer.