A steady layered organic-inorganic perovskite hybrid containing Fe3+ was prepared in the air with phenosafranine as organic sheets, the Fe(CN)63- as inorganic sheets. We utilized the Fe(CN)63- as inorganic sheets of perovskite hybrids, which may help to stabilize the unusual metal-deficient layered structures. The results of X-ray diffractometry (XRD) and scanning electron microscopy (SEM) show that the hybrid is typical layered perovskite structure. The hybrid was mixed with paraffin to form a hybrid paste for the hybrid paste electrode. Electrochemical characteristics of carbon paste electrode (CPE) modified by hybrid were investigated with cyclic voltammetry. The modified electrode can accelerate the electron-transfer to improve the electrochemical reaction reversibility and be use for the determination of chemicals. The interactions between sodium nitrite (NaNO2), sodium bromide (NaBr), hydroxylammonium chloride (NH2OH·HCl), hydroquinone (C6H6O2) with hybrid were studied. The modified electrode exhibits good electrochemical activity. The hybrid can be used as electrochemical materials.