In this paper, B-site doping of an optimized A-site deficient composition, calcium-doped lanthanum strontium titanate, La(0.2)Sre(0.25)Ca(0.45)TiO(3) (LSCTA- with Ni and Fe is presented. The doped compositions were successfully synthesized by the Pechini method and then characterized by XRD, SEM, dilatometry, ac impedance, and dc conductivity. The doped analogues preserved the orthorhombic symmetry of the parent, LSCTA-. The observed dilatometric results were correlated with the particle size. Ac impedance studies revealed their semi-conducting behaviour in air. Furthermore, the doped compositions showed higher conductivity values in reducing atmosphere. Compared to bare pre reduced LSCTA- having conductivity of 38 S cm(-1), the pre reduced 5% Ni doped LSCTA- (LSCTN5) and 5% Fe doped LSCTA- (LSCTF5) showed conductivity values of 47 S cm(-1) and 66 5 cm(-1) at 880 degrees C, respectively. B-site doping could affect the electrical and catalytic properties of LSCTA- materials making them viable alternatives for fuel cell applications. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.