A very simple, as well as sensitive and selective, sensing protocol was developed on a pre-anodized graphite pencil electrode surface coated using poly(thionine) (APGE/PTH). The poly(thionine) coated graphite pencil was then used for simultaneous sensing of 3-nitrophenol (3-NP) and 4-nitrophenol (4-NP). The poly(thionine) coated electrode exhibited an enhanced electrocatalytic property towards nitrophenol (3-NP and 4-NP) reduction. Redox peak potential and current of both nitrophenols were found well resolved and their simultaneous analysis was studied. Under optimized experimental conditions, APGE/PTH showed a long linear concentration range from 20 to 230 nM and 15 nM to 280 nM with a calculated limit of detection (LOD) of 4.5 and 4 nM and a sensitivity of 22.45 µA/nM and 27.12 µA/nM for 3-NP and 4-NP, respectively. Real sample analysis using the prepared sensor was tested with different environmental water samples and the sensors exhibited excellent recovery results in the range from 98.16 to 103.43%. Finally, the sensor exposed an promising selectivity, stability, and reproducibility towards sensing of 3-NP and 4-NP.