A conducting poly(azomethine)ester was prepared by solution phase polycondensation of a preformed Schiff base, 4‐((4‐(4‐(4‐hydroxybenzlideneamino) phenoxy)phenylimino)methyl)phenol and isophthaloyl chloride (I). Different aliphatic/aromatic moieties were incorporated for examining their effect on the electronic properties of material. The resulting polymers (10−4 to 25 S cm−1) were doped with silver (10−6 to 10−2 S cm−1) and blended with polyaniline (10−1 to 13.4 S cm−1) to enhance their electrical conductivity. Polymer/polyaniline blends had superior conductivity even at low polyaniline concentration relative to the silver‐doped chains. The data obtained experimentally were complemented by density function theory at the 6–31G/B3LYP level. The results showed that ΔE along with lowest unoccupied molecular orbital and highest occupied molecular orbital electron density accounts for the electrical properties. Spectroscopic (1HNMR, FTIR) and elemental analysis were used for structural elucidation. Structure–property relation in term of WXRD, SEM‐EDX, atomic force microscope, LLS, and thermal behavior was studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40698.