A composite sensing film (PGS), consisting of poly(N-isopropylacrylamide)101-b-poly(2-acrylamidoethyl benzoate)37 (PNIPAM101-b-PAAEB37), graphene oxides (GO) and short multi-walled carbon nanotubes (SMWCNs), was fabricated and modified onto a working electrode. The sensing film served as a reversible switch for electrochemical detection, with the switching behaviour responding to thermal stimuli. Cyclic voltammetry of hydroquinone (HQ) and catechol (CC) at the PGS film-modified electrode displayed large peak currents when the temperature was above the lower critical solution temperature (LCST) of PNIPAM101-b-PAAEB37. These large currents disappeared at low temperature. Interestingly, the composite film showed reversed electrochemical “on/off” behaviour as compared to previously reported switchable electrodes, which were modified only with temperature-responsive polymers. This behaviour can be attributed to the temperature-dependent phase transition of PNIPAM101-b-PAAEB37 and cooperative effects of the other two functional components (SMWCNs and GO). The repeatable “on/off” switching of the voltammetric responses of HQ/CC on the PGS-modified electrode were achieved via regulating the solution temperature. This research provides a new type of temperature-controlled switchable electrode with potential applications in the design of novel sensors, fuel cells and electronics.