In this work, we report an easy environmental friendly route to synthesize a water-insoluble β-cyclodextrin (β-CD)/graphene oxide (GO) or reduced graphene oxide (rGO) nanocomposite polymers. These nanocomposite hydrogels were synthesized by in-situ melt polymerization, at first the β-CD was covalently binding with GO to produce β-CD/GO and then β-CD/rGO was obtained through in-situ reduction of GO by hydrazine. These hybrid materials were polycondensed in the presence of melted citric acid (CT) as a crosslinker. The structure of achieved macromolecules were characterized by ATR-FTIR, Raman spectroscopy, TGA, DTG, DSC, DDSC, XRD, SEM, EDAX, electrochemical impedance spectroscopy and also by determining the amount of acidic groups and adsorption toward cationic methylene blue. These data have been confirmed that β-CD/GO or rGO effectively polymerized using CT through ester linkage. Swelling ratio data shows ability of these nanocomposites to absorb lots of amount water in their structures and β-CD polymer/rGO (CDP-CT/rGO) gels have higher equilibrium swelling ratio than the corresponding β-CD polymer (CDP-CT) and CDP-CT/GO. The deduced results of cyclic and differential pulse voltammetry electrochemical revealed that CDP-CT/GO and CDP-CT/rGO nanocomposite hydrogels could exhibit higher electrochemical response toward dopamine, tyrosine and uric acid (biomolecules) in compared to unmodified CDP-CT. In addition, CDP-CT/rGO shows higher response related to CDP-CT/GO, which is probably due to the restoration of a graphitic network after reduction of GO. As a result, the improved electrochemical behaviors of these nanocomposites achievement are due to combination of chemical properties of β-CD, GO or rGO nanosheets, polyester and poly(carboxylic acid).