Two platforms have been developed that can be easily prepared for voltammetric analysis of vitamins B2 (VB2, riboflavin) and B6 (VB6, pyridoxine), which are very important for our health. The first platform was prepared by electrochemically reduction of graphene oxide on the glassy carbon electrode (GCE), while the second platform was prepared by the electrochemical deposition of functionalized multi-walled carbon nanotubes (f-MWCNTs) on the electrode. The prepared f-MWCNTs and electrochemically reduced graphene oxide (ERGO) modified electrodes (GCE/f-MWCNTs and GCE/ERGO) were characterized by field emission-scanning electron microscopy (FE-SEM), Fourier transform infrared (FT-IR) spectroscopy, and various electrochemical techniques. Electrochemical determination of the VB2 and VB6 was performed by differential pulse voltammetry (DPV), which is extensively preferred for quantitative assay. Compared with many modified electrodes in previous studies, and bare GCE, these electrodes revealed the high electrocatalytic performance for detecting VB2 and VB6. Linear range for the VB2 was determined to be 0.004–1.0 µmol L−1 with detection limit (DL) of 1.0 nmol L−1 at the GCE/f-MWCNTs electrode and 0.100–40 µmol L−1 with DL of 16 nmol L−1 at the GCE/ERGO electrode. A linear relation of the VB6 oxidation response for the GCE/f-MWCNTs and GCE/ERGO electrodes was observed in the interval of 8.0–1000 µmol L−1 with DL of 2.8 nmol L−1 and 20–1000 µmol L−1 with DL of 14 nmol L−1, respectively. The feasibility study of the developed sensors was investigated by detecting VB6 and VB2 in commercially available ampoule and tablet samples. Moreover, these sensors showed the wide linear range, good selectivity ability, reproducibility, and repeatability.