In the present paper, three electrodes were prepared with the aim of detecting chromium (III) in pharmaceutical tablets and comparing their capabilities and efficiency. At first, N-(pyridine-2-ylcarbamothioyl) benzamide (NP2YCTB) was synthesized and characterized by 1H NMR, FTIR, and 13C NMR spectroscopy methods. Then, it is used as a sensing material to prepare three types of chromium potentiometry sensors including solid-state electrodes (SSE), coated wire electrodes (CWE) as asymmetric electrodes, and liquid membrane electrodes (LME) as symmetric electrodes. The responses of all electrodes were Nernstian. Field-emission scanning electron microscopy was utilized to investigate the liquid membrane morphology. The presence of chromium (III) in the membrane was proved using Energy-dispersive X-ray spectroscopy and the coordination of NP2YCTB heteroatoms with chromium (III) was confirmed by Fourier transform infrared spectroscopy. The limit of detection for SSE (3 × 10−9 mol/L) was enhanced compared with LME (7 × 10−6 mol/L) and CWE (3 × 10−7 mol/L). The response time of electrodes was very short so it was about 5–6 s for LME and CWE and 5–8 s for SSE. The sensors were used for the potentiometric determination of chromium (III) in pharmaceutical tablets and in the potentiometric titration of it with EDTA.