Detection of hydrazine (HZ) in food and environmental samples is of immense importance. The development of a highly sensitive, inexpensive, and rapid electrochemical method for the detection of HZ remains a formidable challenge in the field of electrochemical sensors. In this study, we developed a polyanilineanchored cerium tungstate (PANI@CeW) nanostructure prepared using in situ electrodeposition onto a screen-printed electrode (SPE) surface (PANI@CeW/SPE) for the electrochemical detection of HZ. The synergistic effect between PANI and cerium tungstate nanostructures showed an excellent electrochemical response toward HZ oxidation and linear concentrations of 10− 800 and 50−950 nM with a detection limit of 3.5 and 15 nM for amperometry and DPV methods, respectively. The developed electrode facilitates the real-time detection of HZ in kelp, fish, and drinking water samples. The results obtained using the developed electrode were cross-validated using high-performance liquid chromatography analysis. This report provides direction for the development of electrochemical sensors toward the detection of HZ in food and environmental samples.