Thermoresponsive brushes with a tunable structure are grafted in a controlled way to gold substrates, exploiting an initiator-transfer-terminator agent (iniferter)-based photopolymerization (see figure). The chain length of the polymers is controlled by using UV light as a trigger and the end groups exposed are shown to be easily exchangeable following the grafting process. Reversible volume shrinkage/expansion, roughening, and variation of adhesion are observed.