A series of high‐performance polycarbonates have been prepared with glass‐transition temperatures and decomposition temperatures that are tunable by varying the repeat‐unit chemical structure. Patterning of the polymers with extreme UV lithography has been achieved by taking advantage of direct photoinduced chain scission of the polymer chains, which results in a molecular‐weight based solubility switch. After selective development of the irradiated regions of the polymers, feature sizes as small as 28.6 nm have been printed and the importance of resist‐developer interactions for maximizing image quality has been demonstrated.