This work describes the voltammetric investigation of trace amounts of pain reliever drug methocarbamol (MET) by carbon nanotubes decorated methyl orange polymerized pencil graphite electrode (poly(MO)/CNT@PGE). The proposed modified electrode was prepared by electropolymerization of methyl orange (MO) over the carbon nanotubes (CNTs) decorated on PGE. The geomorphologies of the equipped sensors were accomplished by scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX) and electrochemical impedance spectroscopy (EIS) study. The electrochemical behaviour of MET in presence of levofloxacin (LVF) has been studied by applying different voltammetric techniques in 0.1 M PBS of pH 4.0. The proposed poly(MO)/CNT@PGE shows enhanced peak current with a small negative shift in peak potential for MET over the bare and modified electrodes due to the electrocatalytic features of the modifiers. The different parameters such as effect of polymer layers, pH, scan rate, concentrations, simultaneous and selectivity study for MET were studied by cyclic voltammetry (CV), linear sweep voltammetry (LSV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV). The computed limit of detection (LOD) for MET at different concentrations (10.0–110.0 µM for DPV and 1.0–12.0 µM for SWV) was found to be 5.24 µM and 0.69 µM, respectively. The adapted electrode exhibits special characteristic features such as stability, repeatability, reproducibility, fast electron transfer behaviour and charge transfer resistance (Rct). Based on the results obtained, number of electrons (n), number of protons (m), heterogeneous rate constant (ko) and surface concentration (Γ0) of MET have been calculated by using relative formulae. The selectivity and applicability of the modified electrode were premeditated by real sample investigation of MET present in pharmaceutical tablets with good recovery results to confirm the analytical pertinence of the proposed sensor.