The successful selective metal deposition using a photolabile polymer consisting of a diazosulfonate side chain group has been reported. In addition to 20 mol% diazosulfonate monomer the terpolymer contains 5 mol% of a silane compound, which is necessary for the covalent anchoring of the film onto the substrate. Furthermore, films were prepared using photolabile polymers containing protected amines onto glass and silicon substrates. These films are suitable for imagewise structuring by UV‐light and laser irradiation, and nanoelements like DNA strands could be attached individually in further steps. These polymeric amines with similar structure like the diazosulfonate terpolymers were synthesized by free radical polymerization of three monomer units which are methyl methacrylate (MMA) (spacer), 3‐(trimethoxysilyl)propylmethacrylate (anchoring group) and N‐(N‐nitroveratryloxycarbonyl‐aminopropyl)‐methacrylamide (photolabile compound). The anchoring groups were varied to enable covalent attachment of the polymers, for example, onto gold substrates. Azosulfonates, sulfonate esters, and both protected amines and carboxylic acid groups were used as thermally labile or photolabile functionalities. Selective deprotection using heat or light could be varied. Finally block copolymers based on orthogonally protected hydroxystyrenes could be prepared by controlled radical polymerization. A highly ordered nanostructure could be realized in thin films of these polymers exhibiting strong changes using heat or light treatment. Copyright © 2006 John Wiley & Sons, Ltd.