Aquotris(benzotriazole)sulfatocopper(II).benzotriazole (BTAH-Cu2+) framework was assembled (exploiting pi-pi interactions) on MWCNTs modified glassy carbon electrode (GCE/MWCNTs@BTAH-Cu2+) for efficient sensing of hydrogen peroxide in pH 7 phosphate buffer solution (PBS). The modified electrodes showed stable and well-defined surface confined redox peak at an apparent electrode potential, E-o' = -182 mV vs. Ag/AgCl with surface excess value of 5.519 nmol cm(-2). Structural, physicochemical and electrochemical characterizations of modified electrodes by single crystal XRD, FESEM, Raman spectroscopy, FTIR, QCM and control electrochemical experiments revealed the crystal structure of BTAH-Cu2+ and it's adsorption on MWCNTs. Highly redox active GCE/MWCNTs@BTAH-Cu2+ showed excellent H2O2 sensing in comparison to GCE/BTAH-Cu2+ in pH 7 PBS highlighting the importance of MWCNTs. Amperometric i-t sensing of H2O2 on MWCNTs@BTAH-Cu2+ revealed suitability of this sensor for the linear range, 20-200 mu M. The sensitivity and detection limit values are 0.153 A M-1 cm(-2) and 3.3 mu M respectively. Koutecky-Levich analysis of H2O2 reduction reaction on GCE/MWCNTs@ BTAH-Cu2+ confirms the two electron reduction reaction of H2O2. The ability of the MWCNTs@BTAH-Cu2+ for routine analyses was demonstrated by employing this sensor for H2O2 detection in commercial cosmetic samples. (C) 2017 The Electrochemical Society. All rights reserved.