Thermo-, pH- and electrochemical-sensitive cellulose graft copolymers, hydroxypropylcellulose-g-poly(4-vinylpyridine)-Os(bipyridine) (HPC-g-P4VP-Os(bpy)) were synthesized and characterized. The electrochemical properties of the resulting material were investigated via cyclic voltammetry by coating the graft copolymers on the platinized carbon electrode. The results indicated that the electrochemical properties of the graft copolymer modified electrode were responsive to the pH values of the electrolyte solution. The reversible transformation between the active and inactive state originated from the changes in the architecture of the HPC-g-P4VP-Os(bpy) graft copolymer at different pH values. At high pH (e.g. above the pKa of P4VP), the chains of P4VP collapsed and the electrochemical activity of the electrode was reduced. With immobilization of glucose oxidase (GOx) on the graft copolymer decorated electrode, a biosensor for glucose detection was prepared. The current of the biosensor depended on the glucose concentration in the detected solution and increased with the successive addition of glucose.