In this paper, a novel synthesis of polyethylene glycol (PEG)-modified polypyrrole (PPy) nanomaterials is demonstrated by combining reversible addition-fragmentation chain transfer polymerization and oxidative polymerization. Dye molecules with a heat-labile linker are used as a model drug and covalently anchored onto the PEGlated PPy nanomaterials via "click chemistry." The strong absorption of such PPy nanomaterials in the near-infrared region endows the system excellent photothermal effect, which can be used not only as efficient photothermal agents for photothermal therapy but also good controllers of a drug-release system by retro D-A reaction.