Using nitrate-citrate method the derivatives of layered neodymium–barium cobaltite with entropy stabilized barium and cobalt sublattices were synthesized, their crystal structure, oxygen nonstoichiometry, microstructure, thermal, mechanical and electrotransport properties were investigated. It was found, that increasing of configurational entropy (CE) of barium sublattice (BS) results in shrinkage of perovskite unit cell, lowering oxygen deficiency, porosity, linear thermal expansion coefficient (LTEC, αT) and Seebeck coefficient of the samples, and increasing of their microhardness, thermal stability and electrical conductivity, which is mostly pronounced at transition from low-entropy (LE) BS to the middle-entropy (ME) one. The highest electrical conductivity and lowest LTEC value demonstrates NdBa1/4Sr1/4Ca1/4Mg1/4Fe2/3Co2/3Cu2/3O6–δ compound possessing the highest CE – ≈ 200 S·cm–1 at 1015 K and 16.2·10–6 K–1 within temperature range of 350–1070 K, which is almost 10 times larger and 13 % less respectively than for NdBaFe2/3Co2/3Cu2/3O6–δ layered perovskite.