Abstract The thermo-responsive behavior of polymer films consisting of novel linear triblock copolymers of poly(n-butyl methacrylate)–poly(methyl methacrylate)–poly(2-fluoroethyl methacrylate) (PnBuMA–PMMA–P2FEMA) are reported using differential scanning calorimetry (DSC), atomic forcing microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contacting angle (CA) measurements. The surface morphology, wettability and chemical structure of thin films of these triblock copolymers on silicon wafers as a function of temperature have been investigated. It has been shown that the wettability of the films is thermally switchable. Detailed structural analysis shows that thermo-responsive surface composition changes are produced. The underlying mechanism of the thermoresponsive behavior is discussed.