Cadaverine and putrescine are well known biogenic amines for food spoilage, their presence along with histamine increases the food toxicity to manifold and rapid detection of these analytes remains challenging. To address these problems, poly(neutral red) (PNR) based electrochemical sensor for sensing of cadaverine and putrescine has been developed. Neutral red (NR) polymerised over glassy carbon electrode (GCE) has been utilized for sensing of biogenic amines. Positively charged groups on PNR/GCE surface forms ion-pair complex with putrescine or cadaverine via diphosphate ion bridging which facilitates the sensing ability and the formation of ion-pair, as evidenced by DFT calculations. PNR/GCE exhibited detection ability in the range of 0.025 to 414 μM with a limit of detection of 0.22 μM and 0.25 μM for cadaverine and putrescine, respectively. The developed non-enzymatic electrochemical sensor for cadaverine and putrescine exhibited good anti-interference ability towards common ions and amino acids were studied. Demonstrated non-enzymatic electrochemical sensor method is simple and convenient for tracing biogenic amines in real samples like spoilage in fish specimen.