In this article, poly(1,2-diaminoanthraquinone) (pDAAQ) and poly(1,5-diaminonaphthalene) (pDAN) were electrochemically deposited layer by layer on a glassy carbon electrode (GCE) to generate pDAAQ/ pDAN@GCE and pDAN/pDAAQ@GCE composite electrodes, respectively. The morphology and characteristics of the modified electrodes were investigated via electrochemical impedance spectroscopy)EIS), Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy)SEM). The obtained results reveal the outstanding performance of the pDAN/ pDAAQ@GCE electrode for electrochemical nitrite sensing where pDAAQ plays a vital role as the inner layer. Cyclic voltammetry (CV), linear sweep voltammetry (LSV), and differential pulse voltammetry (DPV) measurements revealed that the oxidation peak current of nitrite was proportional to its concentration. The best LSV results were obtained in a concentration range of 10-150 μM, with a limit of detection of 1.2 μM. Furthermore, the pDAN/pDAAQ@GCE composite electrode was used to determine nitrite ions in real water samples with good results.