Green analytical procedures are gaining popularity in the pharmaceutical research area as a way to reduce environmental impact and improve analyst health safety. The current work presents a green and sensitive electrochemical carbon paste electrode that has been chemically modified with zirconium dioxide and multi-walled carbon nanotubes for estimation of pyridoxine HCl (PYR) and doxylamine succinate (DOX) using the square wave voltammetric technique. Under optimum conditions, the linearity ranges were 20.00–2000.00 ng mL−1 and 2.00–20.00 µg mL−1 for both drugs in the 1st linear segment and 2nd linear segment, respectively. Stability testing assesses how the quality of a drug substance changes over time, depending on environmental and laboratory factors. DOX was found to undergo oxidative degradation when refluxed for 7 h using 30% H2O2 and the degraded product (DOX DEG) (toxic metabolite) was successfully characterized utilizing LC–MS. The developed electrode showed selectivity for the determination of binary mixture in pure form, pharmaceutical form, and in the presence of DOX DEG and common interfering molecules with good recovery. The proposed method was found to be eco-friendlier than the reported method in terms of the use of hazardous chemicals and solvents, energy consumption, and waste generation.Graphical