Nonlead perovskite type, Ba(Cu1/3Nb2/3−xWx)O3 (x = 0, 0.025), ferroelectric ceramic powders (BCN) were prepared by the microwave-assisted citrate-nitrate sol-gel technique. The gel was formed from a stable and homogeneous sol prepared by mixing stable solutions of barium- and copper-nitrate, tungsten citrate, and peroxo-citrato-niobium precursors. Microwave irradiation of the gel resulted in a dark, fluffy precursor material after auto-combustion. Calcination of the as-combusted samples produces a single phase with tetragonal splitting in X-Ray diffraction patterns. The crystallite size of the synthesized samples was found to be 41 nm. Particle morphology and the size of nanocrystalline powders were characterized by scanning electron microscopy and photon correlation spectroscopy, respectively. Electrical and dielectric properties of sintered samples were investigated by impedance spectroscopy. The isothermal ac measurements were performed from room temperature, up to 600 °C for W6+ doped and undoped BCN samples.