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This paper describes the synthesis of ZnO/MWCNT nanocomposite, and their potential application in photoelectrochemical (PEC) water splitting for hydrogen generation and photocatalytic degradation of methylene blue dye. For the synthesis of nanocomposite, ZnO nanoparticles were grown on the MWCNT surface by a simple chemical route. Microscopic studies showed that ZnO nanoparticles were well dispersed on the MWCNT surface and Raman study confirmed the intimate integration between ZnO and MWCNT. The nanocomposite exhibit higher photocatalytic degradation of methylene blue dye as compared to bare ZnO. The ZnO/MWCNT photoanode shows ∼5 times increase in photocurrent density in comparison to pure ZnO, at an applied potential of +1 V vs. Ag/AgCl. The enhanced photocurrent density of ZnO/MWCNT photoanode is attributed to the decrease in band-bending and effective interfacial electron transfer due to the conducting CNT scaffold, which facilitates the charge collection and charge transport in the ZnO/MWCNT nanocomposite. The Electrochemical impedance spectroscopy measurements confirmed the faster charge transfer at the interface in the case of nanocomposite. These results suggest substantial potential of ZnO/MWCNT nanocomposite in dye degradation and PEC water splitting applications. [ABSTRACT FROM AUTHOR]