In this study nickel and boron doped sodium cobalt oxide NaCo2-xNixByO4 (0 <= x <= 0.3, 0 <= y <= 0.1) nanocrystalline thermoelectric ceramic powders were synthesized using electrospinning techniques and then consolidated into bulk ceramics. The differences in the microstructure and thermoelectric properties of the samples as a result of doping effect have been investigated. The crystalline structures of the powders and nanofibers were characterized using Xray diffraction and scanning electron microscopy and BET Analysis before and after the calcination process at different temperatures. Nanofibers prepared by the use of electrospinning technique, have a diameter of approximately 300 nm, and the diameter of the grains of calcined powders was observed to range between 150 to 500 nanometers. Thermoelectric properties of the bulk ceramics were measured by physical properties measurement system (Lot-Oriel PPMS) in a temperature range of 15-300 K. The calculated values of dimensionless figure of merit at 300 K are 4.25 x 10(-5), 5.3 x 10(-6), 8.6 x 10(-5) and 9 x 10(-6) for sintered powders from undoped, Ni and B doped powders, respectively.