A thermo-sensitive graphene-based hybrid is prepared by the electrostatic interactions between the poly(diallyldimethylammonium chloride)-co-poly(N-isopropylacrylamide) (PDDA-co-PNIPAM) and graphene oxide (GO). The electrostatic interaction, chemical structure, morphology and thermo-sensibility of the hybrid are systematically characterized, which have been manifested that the electrostatic interaction between the PDDA-co-PNIPAM and GO is strong, and the employment of the cationic PDDA-co-PNIPAM results into a well distributed polymer nanoparticles on the GO sheets. The new PDDA-co-PNIPAM/GO hybrid has good dispersity in some polar solvents. Notably, the phase transition of this hybrid can be reversibly modulated by temperature in water, which can be applied as thermo-switch material for the adsorption and separation of the organic pigments in aqueous solutions.