Steady organic-inorganic perovskite hybrids with (H22-Ap)3/2Fe(CN)6, (H23-Ap)3/2Fe(CN)6 and (H24-AP)3/2Fe(CN)6 (2-AP = 2-aminopyridine, 3-AP = 3- aminopyridine, 4-AP = 4- aminopyridine) were formed from aqueous solution. Each structure was an unusual layered organic-inorganic structural type. A device was designed to construct electrochemical sensing devices using above organic-inorganic perovskite hybrids. The sequence of redox activity is (H24-Ap)3/2Fe(CN)6 > (H22-Ap)3/2Fe(CN)6 > (H23-AP)3/2Fe(CN)6 and that of electrocatalytical activity is (H22-Ap)3/2Fe(CN)6 > (H23-Ap)3/2Fe(CN)6 > (H24-AP)3/2Fe(CN)6. The variation coefficients (RSD) of successive and interval assays are less than 2.0%. Three electrochemical sensing devices display a remarkable electrochemical sensitivity and stability.