New Schiff-base polyesters were prepared from a dihydroxy monomer (E)-1-(5-(4-hydroxy-3-chlorobenzylidene)thiocarbamoylaminonaphthyl)-3-(4-hydroxy-3-chlorobenzyli-dene)thiourea. The processable pyridine or thiophene-based poly(azomethine–ester)s (PAEs) possess high molar mass of 111 x 10³–127 x 10³ g mol^-1. The 10% weight loss (521–527°C) and glass transition temperature (287–291°C) depicted high thermal stability. Polyaniline (PAN) doped with dodecylbenzenesulfonic acid (PAN/DBSA), prepared by in situ doping polymerization, was blended in solution/melt with PAEs. Field emission scanning electron microscopy of melt blended PAEs/PAN/DBSA showed nanolevel homogeneity of microstructure accountable for superior electrical conductivity (1.9–2.8 S cm^-1). The miscible nanoblends also exhibited high heat stability (T₁₀; 500–507°C) and mechanical strength (45.51–48.17 MPa) relative to reported azomethine/PAN-based structures.