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Fabrication of conducting polymer networks based on polypyrrole/multi‐walled carbon nanotubes (PPy/MWCNTs) modified graphite electrodes that were achieved with a single‐step electropolymerization and potential use of these electrodes for deoxyribonucleic acid (DNA) recognition and anticancer drug (Paclitaxel, PTX) quantification were presented in the present work. PPy/MWCNTs nanohybrid PGEs were constructed in aqueous solution of pyrrole (Py) and MWCNTs using cyclic voltammetry (CV) and constant potential electrolysis. So‐formed electrodes were characterized with cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Surface morphologies of the surfaces were investigated by scanning electron microscopy (SEM) studies. Bio‐application of the PPy/MWCNTs nanohybrid modified PGEs were accomplished by subjecting them to double‐stranded DNA (dsDNA) modification for direct DNA recognition and PTX determination. For the drug determination, interaction of DNA‐based electrodes with PTX was investigated. Detection limit was found as 1.55 x 10−8 M based on the changes in the oxidation of guanine base which made the proposed electrode convenient for clinical trials. [ABSTRACT FROM AUTHOR]